CN110062976A

CN110062976A - Electrolyte, electrochemical appliance, lithium ion secondary battery and component

Info

Publication number: CN110062976A
Application number: CN201780075899.5A
Authority: CN
Inventors: 山崎穣辉; 高桥谦三; 有马博之; 坂田英郎; 木下雅量; 木下信一
Original assignee: Daikin Industries Ltd
Current assignee: Daikin Industries Ltd
Priority date: 2016-12-26
Filing date: 2017-11-01
Publication date: 2019-07-26
Anticipated expiration: 2037-11-01
Also published as: US20200020982A1; EP3522288A1; JPWO2018123259A1; WO2018123259A1; CN110062976B; JP6795041B2; US11043698B2; EP3522288A4

Abstract

The present invention is not easy to reduce providing a kind of residual capacity when storing at high temperature, resistance increment rate also not labile electrolyte.The feature of the electrolyte is to contain: by general formula (1): R¹¹CFX¹¹(CH₂)_n11COOR¹²Expression compound (1) (in formula, R¹¹For H, F, carbon atom number be 1~3 non-fluoro-alkyl or carbon atom number be 1~3 fluoro-alkyl, X¹¹For H or F, R¹²For carbon atom number be 1~3 non-fluoro-alkyl or carbon atom number be 1~3 fluoro-alkyl, the integer that n11 is 0~3), fluoro carbonic ester and specific additive.

Description

Electrolyte, electrochemical appliance, lithium ion secondary battery and component

Technical field

The present invention relates to electrolyte, electrochemical appliance, lithium ion secondary battery and components.

Background technique

Along with the lightweight of electronic product in recent years, miniaturization, has the lithium ion secondary battery of high-energy density Exploitation promoting.In addition, the expansion of the application field with lithium ion secondary battery, needs to carry out changing for battery behavior It is kind.In particular, battery behavior becomes more and more important from now on when lithium ion secondary battery is used for vehicle-mounted.

In patent document 1, it discloses containing light gold represented by compound represented by chemical formula 1 and chemical formula 2 Belong to the electrolyte that salt is characterized.

[changing 1]

(in formula, the alkyl or its at least part of hydrogen that R31 indicates hydrogen-based, fluorine-based or carbon atom number is 1~3 are replaced by fluorine Obtained from group, X31 indicate hydrogen-based or fluorine-based, R32 indicate carbon atom number be 1 or 2 alkyl.)

[changing 2]

(in formula, (R21 indicates alkylidene, halogeno alkylen, arlydene or halogen to R11 expression-C (=O)-R21-C (=O)-group For arlydene) or-C (=O)-C (=O)-group, R12 indicates halogen, alkyl, halogenated alkyl, aryl or halogenated aryl, X11 with And X12 respectively indicates oxygen (O) or sulphur (S), M11 indicates transition metal element or 3B race element, 4B in short cycle type periodic table Race's element or 5B race element, M21 indicate that 1A race element or 2A race element or aluminium (Al) in short cycle type periodic table, a are 1~4 Integer, b be 0~8 integer, c, d, e and f are respectively 1~3 integer.)

Patent Document 2 discloses a kind of non-aqueous containing solvent for dissolving electrolyte salt (I) and electrolytic salt (II) It is electrolyte, the solvent for dissolving electrolyte salt (I) is contained by following formula (A) fluorine-containing ester solvent (A) indicated and except aforementioned Fluoride solvent (B) other than fluorine-containing ester solvent (A).

R¹CFXCOOR² (A)

(in formula, R¹The alkyl that can be replaced by fluorine atoms of hydrogen atom for being 1~3 for hydrogen atom, fluorine atom or carbon atom number；X is hydrogen Atom or fluorine atom；Wherein, work as R¹X is hydrogen atom when for fluorine atom or perfluoroalkyl；R²The alkyl for being 1~4 for carbon atom number.)

In patent document 3, it discloses and contains the non-aqueous electrolyte for secondary battery of lithium salts electrolyte in non-aqueous solvent； Contain the fluoro chain carboxylate and film forming compound indicated by following formula (1), the film forming chemical combination in above-mentioned non-aqueous solvent Object the range of+1.0~3.0V can decompose on the basis of by the equilibrium potential of lithium metal and lithium ion.

R1-CH₂-COO-R2 (1)

(in formula, R1 indicates that hydrogen or alkyl, R2 indicate alkyl, and the sum of carbon atom number in R1 and R2 is within 3；When R1 is hydrogen At least part of hydrogen in R2 is replaced by fluorine, and at least part of the hydrogen when R1 is alkyl in R1 and/or R2 is taken by fluorine Generation.)

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2005-317446 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2008-257988 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2009-289414 bulletin

Summary of the invention

Problems to be solved by the invention

However, existing electrolyte has the following problems: it is deteriorated during storage, it is remaining compared with immediately after preparation Capacity reduces, resistance increment rate increases.In the case where storing at high temperature, the bad of existing electrolyte is observed especially significantly Change.

Even if the present invention is made in view of above-mentioned status, and it is an object of the present invention to provide a kind of residual capacity when storing at high temperature Also it is not easy to reduce, resistance increment rate also not labile electrolyte.

A technical solution to solve project

The present invention relates to a kind of electrolyte, which is characterized in that contains:

By general formula (1): R¹¹CFX¹¹(CH₂)_n11COOR¹²Expression compound (1) (in formula, R¹¹For-H ,-F, carbon atom number be 1~ The fluoro-alkyl that 3 non-fluoro-alkyl or carbon atom number is 1~3, X¹¹For-H or-F, R¹²It is not 1~3 not for carbon atom number The fluoro-alkyl that fluoro-alkyl or carbon atom number are 1~3, the integer that n11 is 0~3),

Fluoro carbonic ester, and

Selected from by having additive (II), general formula represented by the additive (I) of the structure represented by leading to formula (I), logical formula (II) (III) additive (III) represented by, the additive (IV) with structure represented by any one in logical formula (IV), with And at least one kind of additive in the group of additive represented by logical formula (V) (V) composition.

Logical formula (I):

[changing 3]

Logical formula (II):

[changing 4]

(in formula, X¹³~X¹⁶It is identical or different, respectively indicate-H ,-CH₃,-F, the fluoro-alkyl that can have ehter bond or can have There is the fluoroalkyl of ehter bond.Wherein, X¹³~X¹⁶In at least one be-F, can have the fluoro-alkyl of ehter bond or can have There is the fluoroalkyl of ehter bond.)

Logical formula (III):

[changing 5]

(in formula, X¹⁷And X¹⁸It is identical or different, respectively indicate-H ,-CH₃,-F, the fluoro-alkyl that can have ehter bond or can Fluoroalkyl with ehter bond.Wherein, X¹⁷And X¹⁸In any one for-F, can have ehter bond fluoro-alkyl or There can be the fluoroalkyl of ehter bond.)

Logical formula (IV):

Any one in-C ≡ N ,-N=C=O and following [changing 6], [changing 7] and [changing 8] is by the structure that indicates.

[changing 6]

[changing 7]

[changing 8]

Logical formula (V):

[changing 9]

(in formula,

A^a+For metal ion, hydrogen ion or ion.The integer that a is 1~3, the integer that b is 1~3, p b/a, n²³It is 1~4 Integer, n²¹For 0~8 integer, n²²It is 0 or 1, Z²¹For transition metal, the III group of the periodic table of elements, IV race or V group element.

X²¹For O, S, carbon atom number be 1~10 alkylidene, carbon atom number be 1~10 halogeno alkylen, carbon atom number 6 ~20 arlydene or carbon atom number be 6~20 halogenated arlydene (alkylidene, halogeno alkylen, arlydene and Halogenated arlydene can have substituent group, hetero atom in its structure, work as n²²For 1 and n²³N when being 2~4²³A X²¹It can key each other It closes).

L²¹For halogen atom, cyano, carbon atom number be 1~10 alkyl, carbon atom number be 1~10 halogenated alkyl, carbon atom number For 6~20 aryl, carbon atom number be 6~20 halogenated aryl (alkylidene, halogeno alkylen, arlydene and halogenated Arlydene can have substituent group, hetero atom in its structure, work as n²¹N when being 2~8²¹A L²¹Can bond together to form ring) or- Z²³Y²³。

Y²¹、Y²²And Z²³It is independently of one another O, S, NY²⁴, alkyl or fluoro alkyl.Y²³And Y²⁴Be independently of one another H, F, The aryl or carbon that halogenated alkyl that alkyl that carbon atom number is 1~10, carbon atom number are 1~10, carbon atom number are 6~20 are former (alkyl, halogenated alkyl, aryl and halogenated aryl can have substitution to the halogenated aryl that subnumber is 6~20 in its structure Base, hetero atom, when there are multiple Y²³Or Y²⁴When can bond together to form ring).)

Above-mentioned fluoro carbonic ester is preferably selected from by fluoro saturated cyclic carbonic ester (but except additive (II)) and fluorine For at least one kind of in the group of linear carbonate composition.

Above-mentioned additive is preferably selected from by additive (I), additive (III), additive (IV) and additive (V) It is at least one kind of in the group of composition.

It is preferred that above-mentioned fluoro carbonic ester is fluorinated chain carbonate, above-mentioned additive is additive (II).

The present invention also relates to a kind of electrochemical appliance or lithium ion secondary batteries, which is characterized in that has above-mentioned electrolyte.

The present invention also relates to a kind of components, which is characterized in that has above-mentioned electrochemical appliance or above-mentioned lithium ion secondary Battery.

Invention effect

Even if electrolyte of the invention is stored at high temperature, residual capacity is also not easy to reduce, resistance increment rate is also not easy Variation.

Specific embodiment

In the following, the present invention is specifically described.

Electrolyte of the invention contains compound (1), fluoro carbonic ester and additive.

Compound (1) is by general formula (1): R¹¹CFX¹¹(CH₂)_n11COOR¹²It indicates.

(in formula, R¹¹For-H ,-F, carbon atom number be 1~3 non-fluoro-alkyl or carbon atom number be 1~3 fluoro-alkyl, X¹¹For-H or-F, R¹²For carbon atom number be 1~3 non-fluoro-alkyl or carbon atom number be 1~3 fluoro-alkyl, n11 For 0~3 integer.)

As R¹¹, it is preferably selected from by-H ,-F ,-CH₃、-CHF₂、-CH₂F and-CF₃It is at least one kind of in the group of composition.

As R¹², it is preferably selected from by-CH₃And-C₂H₅It is at least one kind of in the group of composition.

As n11, preferably 0~2 integer, more preferable 0 or 1.

As compound (1), it is preferably selected from by CHF₂COOCH₃、CF₃CHFCOOCH₃、CHF₂COOC₂H₅、 CHF₂CF₂COOC₂H₅、CF₃CHFCOOCH₃、CF₃CHFCOOC₂H₅、CH₃CF₂COOCH₃、CH₃CF₂COOC₂H₅、CF₃CH₂COOCH₃With And CF₃CH₂CH₂COOCH₃It is at least one kind of in the group of composition.

As above-mentioned fluoro carbonic ester, it is preferably selected from by fluoro saturated cyclic carbonic ester and fluorinated chain carbonate group At group in it is at least one kind of.Above-mentioned fluoro saturated cyclic carbonic ester is preferably fluoro saturated cyclic carbonic ester (but additive (II) Except).

Above-mentioned fluoro saturated cyclic carbonic ester is the addition saturated cyclic carbonic ester of fluorine atom, specifically, can enumerate by The compound that the following general formula (A) indicates.

[changing 10]

(in formula, X¹~X⁴It is identical or different, respectively indicate-H ,-CH₃、-C₂H₅,-F, the fluoro-alkyl that can have ehter bond or There can be the fluoroalkyl of ehter bond.Wherein, X¹~X⁴In at least one be-F, can have ehter bond fluoro-alkyl or can Fluoroalkyl with ehter bond.)

When containing above-mentioned fluoro saturated cyclic carbonic ester, electrolyte of the invention is in the feelings for being applied to lithium ion secondary battery etc. Under condition, stable overlay film can be formed in cathode, can sufficiently inhibit the side reaction of the electrolyte at cathode.As a result, it is possible to To highly stable and excellent charge-discharge characteristic.

In addition, in the present specification, " ehter bond " refers to the key indicated by-O-.

From the viewpoint of dielectric constant, oxidative resistance are good, X¹~X⁴In 1 or 2 preferably-F, can have ether The fluoro-alkyl of key or the fluoroalkyl that can have ehter bond.

From reduction, the rising of flash-point, the deliquescent raising of even electrolytic salt of the viscosity that can be expected under low temperature Viewpoint is set out, X¹~X⁴Preferably-H ,-F, fluoro-alkyl (a), fluoro-alkyl (b) or fluoroalkyl with ehter bond (c)。

Above-mentioned fluoro-alkyl (a) is base obtained from least one in hydrogen atom possessed by alkyl is replaced by fluorine atoms Group.The carbon atom number of fluoro-alkyl (a) is preferably 1~20, and more preferably 1~17, further preferably 1~7, particularly preferably 1~5.

If carbon atom number excessively becomes larger, low-temperature characteristics may be reduced, and the dissolubility of electrolytic salt may reduce；If carbon is former Subnumber is very few, then it is possible that the deliquescent reduction of electrolytic salt, the reduction of discharging efficiency, even sticky increase etc..

Among above-mentioned fluoro-alkyl (a), it is 1 fluoro-alkyl (a) as carbon atom number, CFH can be enumerated₂-、CF₂H- and CF₃-.Particularly, CF₂H- and CF₃It is preferred in terms of High temperature storage characteristic.

Among above-mentioned fluoro-alkyl (a), the fluoro-alkyl (a) for being 2 or more as carbon atom number, from the dissolution of electrolytic salt Property it is good from the perspective of, preferably enumerate by the following general formula (a-1) indicate fluoro-alkyl.

R¹-R²-(a-1)

(in formula, R¹For that can have the alkyl that the carbon atom number of fluorine atom is 1 or more；R²For that can have the carbon atom number of fluorine atom For 1~3 alkylidene；Wherein, R¹And R²In at least 1 have fluorine atom.)

In addition, R¹And R²Can also have other atoms other than carbon atom, hydrogen atom and fluorine atom.

R¹For that can have the alkyl that the carbon atom number of fluorine atom is 1 or more.As R¹, preferably carbon atom number be 1~16 it is straight The alkyl of chain or branched.As R¹Carbon atom number, more preferable 1~6, further preferred 1~3.

As R¹, specifically, as the alkyl of straight-chain or branched, can enumerate: CH₃-、CH₃CH₂-、CH₃CH₂CH₂-、 CH₃CH₂CH₂CH₂, and

[changing 11]

Deng.

In addition, working as R¹For the straight-chain with fluorine atom alkyl when, can enumerate: CF₃-、CF₃CH₂-、CF₃CF₂-、 CF₃CH₂CH₂-、CF₃CF₂CH₂-、CF₃CF₂CF₂-、CF₃CH₂CF₂-、CF₃CH₂CH₂CH₂-、CF₃CF₂CH₂CH₂-、 CF₃CH₂CF₂CH₂-、CF₃CF₂CF₂CH₂-、CF₃CF₂CF₂CF₂-、CF₃CF₂CH₂CF₂-、CF₃CH₂CH₂CH₂CH₂-、 CF₃CF₂CH₂CH₂CH₂-、CF₃CH₂CF₂CH₂CH₂-、CF₃CF₂CF₂CH₂CH₂-、CF₃CF₂CF₂CF₂CH₂-、CF₃CF₂CH₂CF₂CH₂-、 CF₃CF₂CH₂CH₂CH₂CH₂-、CF₃CF₂CF₂CF₂CH₂CH₂-、CF₃CF₂CH₂CF₂CH₂CH₂-、HCF₂-、HCF₂CH₂-、HCF₂CF₂-、 HCF₂CH₂CH₂-、HCF₂CF₂CH₂-、HCF₂CH₂CF₂-、HCF₂CF₂CH₂CH₂-、HCF₂CH₂CF₂CH₂-、HCF₂CF₂CF₂CF₂-、 HCF₂CF₂CH₂CH₂CH₂-、HCF₂CH₂CF₂CH₂CH₂-、HCF₂CF₂CF₂CF₂CH₂-、HCF₂CF₂CF₂CF₂CH₂CH₂-、FCH₂-、 FCH₂CH₂-、FCH₂CF₂-、FCH₂CF₂CH₂-、FCH₂CF₂CF₂-、CH₃CF₂CH₂-、CH₃CF₂CF₂-、CH₃CF₂CH₂CF₂-、 CH₃CF₂CF₂CF₂-、CH₃CH₂CF₂CF₂-、CH₃CF₂CH₂CF₂CH₂-、CH₃CF₂CF₂CF₂CH₂-、CH₃CF₂CF₂CH₂CH₂-、 CH₃CH₂CF₂CF₂CH₂-、CH₃CF₂CH₂CF₂CH₂CH₂-、CH₃CF₂CH₂CF₂CH₂CH₂-、HCFClCF₂CH₂-、HCF₂CFClCH₂-、 HCF₂CFClCF₂CFClCH₂-、HCFClCF₂CFClCF₂CH₂Etc..

In addition, working as R¹For the branched with fluorine atom alkyl when, preferably enumerate following compounds:

[changing 12]

[changing 13]

Deng.

Wherein, there is CH due to working as₃-、CF₃Viscosity is easy to get higher when such branch, therefore more preferably its quantity few (1 It is a) or be 0.

R²For that can have the alkylidene that the carbon atom number of fluorine atom is 1~3.R²It can be straight-chain, be also possible to branch Shape.The example for constituting the minimum structural unit of alkylidene of such straight-chain or branched is illustrated below.R²Individually by them It constitutes or is made of their combination.

(i) minimum structural unit of straight-chain alkylidene:

-CH₂-、-CHF-、-CF₂-、-CHCl-、-CFCl-、-CCl₂-。

(ii) minimum structural unit of branched alkylidene:

[changing 14]

In addition, among above example, never occur to take off as caused by alkali HCl reaction, it is more stable from the perspective of, it is excellent Choosing is made of the structural unit without Cl.

Work as R²When for straight-chain, R²The minimum structural unit of above-mentioned straight-chain is contained only, wherein it is preferred that-CH₂-、-CH₂CH₂- Or-CF₂-.From the viewpoint of capable of being made further to improve the dissolubility of electrolytic salt, more preferable-CH₂Or-CH₂CH₂-。

Work as R²When for branched, R²Minimum structural unit containing the above-mentioned branched of at least one is preferably enumerated by leading to Formula-(CX^aX^bGroup (the X for)-indicate^aFor H, F, CH₃Or CF₃；X^bFor CH₃Or CF₃.Wherein, X^bFor CF₃When, X^aFor H or CH₃).It is special Not, they can be such that the dissolubility of electrolytic salt further improves.

It as preferred fluoro-alkyl (a), such as can enumerate: CF₃CF₂-、HCF₂CF₂-、H₂CFCF₂-、CH₃CF₂-、 CF₃CHF-、CF₃CF₂CF₂-、HCF₂CF₂CF₂-、H₂CFCF₂CF₂-、CH₃CF₂CF₂, and

[changing 15]

[changing 16]

Deng.

The above-mentioned fluoro-alkyl (b) with ehter bond is at least one quilt having in hydrogen atom possessed by the alkyl of ehter bond Obtained from fluorine atom replaces.The carbon atom number of the above-mentioned fluoro-alkyl (b) with ehter bond is preferably 2~17.If carbon atom number Excessively, then the viscosity of above-mentioned fluoro saturated cyclic carbonic ester improves, in addition, since fluoro-containing group increases, it is possible that dielectric The dissolubility of electrolytic salt caused by the reduction of constant reduces and the reduction of the intermiscibility of other solvents.From this viewpoint, on The carbon atom number for stating the fluoro-alkyl (b) with ehter bond is more preferably 2~10, further preferably 2~7.

The alkylidene for constituting the ether moiety of the above-mentioned fluoro-alkyl (b) with ehter bond can be the Asia of straight-chain or branched Alkyl.The example for constituting the minimum structural unit of alkylidene of such straight-chain or branched is illustrated below.

(i) minimum structural unit of straight-chain alkylidene:

-CH₂-、-CHF-、-CF₂-、-CHCl-、-CFCl-、-CCl₂-。

(ii) minimum structural unit of branched alkylidene:

[changing 17]

Alkylidene can be separately formed by these minimum structural units, can also be by multiple straight-chains (i), multiple branched (ii) or the combination of straight-chain (i) and branched (ii) are constituted.Preferred specific example is described below.

As the further preferred fluoro-alkyl (b) with ehter bond, can enumerate by general formula (b-1):

R³-(OR⁴)_n1- (b-1)

The group of expression.

(in formula, R³For can have fluorine atom, carbon atom number be preferably 1~6 alkyl；R⁴For that can have fluorine atom, carbon original Subnumber is preferably 1~4 alkylidene；The integer that n1 is 1~3；Wherein, R³And R⁴In at least one have fluorine atom.)

As R³And R⁴, following group can be enumerated.Can be appropriately combined by them, constitute the tool indicated by above-mentioned general formula (b-1) There is the fluoro-alkyl (b) of ehter bond.But R³And R⁴It is not limited to following group.

(1) it is used as R³, preferably by general formula: X^c ₃C-(R⁵)_n2Alkyl (3 X indicated^cIt is identical or different, it is H or F；R⁵ The alkylidene with fluorine atom for being 1~5 for carbon atom number；N2 is 0 or 1).

When n2 is 0, as R³, CH can be enumerated₃-、CF₃-、HCF₂And H₂CF-。

As n2 be 1 when specific example, as R³For the group of straight-chain, can enumerate: CF₃CH₂-、CF₃CF₂-、 CF₃CH₂CH₂-、CF₃CF₂CH₂-、CF₃CF₂CF₂-、CF₃CH₂CF₂-、CF₃CH₂CH₂CH₂-、CF₃CF₂CH₂CH₂-、 CF₃CH₂CF₂CH₂-、CF₃CF₂CF₂CH₂-、CF₃CF₂CF₂CF₂-、CF₃CF₂CH₂CF₂-、CF₃CH₂CH₂CH₂CH₂-、 CF₃CF₂CH₂CH₂CH₂-、CF₃CH₂CF₂CH₂CH₂-、CF₃CF₂CF₂CH₂CH₂-、CF₃CF₂CF₂CF₂CH₂-、CF₃CF₂CH₂CF₂CH₂-、 CF₃CF₂CH₂CH₂CH₂CH₂-、CF₃CF₂CF₂CF₂CH₂CH₂-、CF₃CF₂CH₂CF₂CH₂CH₂-、HCF₂CH₂-、HCF₂CF₂-、 HCF₂CH₂CH₂-、HCF₂CF₂CH₂-、HCF₂CH₂CF₂-、HCF₂CF₂CH₂CH₂-、HCF₂CH₂CF₂CH₂-、HCF₂CF₂CF₂CF₂-、 HCF₂CF₂CH₂CH₂CH₂-、HCF₂CH₂CF₂CH₂CH₂-、HCF₂CF₂CF₂CF₂CH₂-、HCF₂CF₂CF₂CF₂CH₂CH₂-、FCH₂CH₂-、 FCH₂CF₂-、FCH₂CF₂CH₂-、CH₃CF₂-、CH₃CH₂-、CH₃CF₂CH₂-、CH₃CF₂CF₂-、CH₃CH₂CH₂-、CH₃CF₂CH₂CF₂-、 CH₃CF₂CF₂CF₂-、CH₃CH₂CF₂CF₂-、CH₃CH₂CH₂CH₂-、CH₃CF₂CH₂CF₂CH₂-、CH₃CF₂CF₂CF₂CH₂-、 CH₃CF₂CF₂CH₂CH₂-、CH₃CH₂CF₂CF₂CH₂-、CH₃CF₂CH₂CF₂CH₂CH₂-、CH₃CH₂CF₂CF₂CH₂CH₂-、 CH₃CF₂CH₂CF₂CH₂CH₂Etc..

It is 1 and R as n2³For the group of branched, can enumerate:

[changing 18]

Deng.

Wherein, there is CH due to working as₃-、CF₃Viscosity is easy to get higher when such branch, therefore R³More preferably straight-chain Group.

(2) above-mentioned general formula (b-1)-(OR⁴)_n1In, the integer that n1 is 1~3, preferably 1 or 2.In addition, working as n1=2 Or when 3, R⁴It can be identical or different.

As R⁴Preferred specific example, the group of straight-chain or branched below can be enumerated.

As the group of straight-chain ,-CH can be enumerated₂-、-CHF-、-CF₂-、-CH₂CH₂-、-CF₂CH₂-、-CF₂CF₂-、- CH₂CF₂-、-CH₂CH₂CH₂-、-CH₂CH₂CF₂-、-CH₂CF₂CH₂-、-CH₂CF₂CF₂-、-CF₂CH₂CH₂-、-CF₂CF₂CH₂-、- CF₂CH₂CF₂-、-CF₂CF₂CF₂Etc..

As the group of branched, can enumerate:

[changing 19]

Deng.

Above-mentioned fluoroalkyl (c) is that at least one in hydrogen atom possessed by alkoxy is replaced by fluorine atoms and obtains Group.Above-mentioned fluoroalkyl (c) preferably carbon atom number is 1~17.More preferable carbon atom number is 1~6.

As above-mentioned fluoroalkyl (c), particularly preferably by general formula: X^d ₃C-(R⁶)_n3Fluoroalkyl (3 of-O- expression X^dIt is identical or different, it is H or F；R⁶Preferably carbon atom number be 1~5 the alkylidene with fluorine atom；N3 is 0 or 1；Its In, 3 X^dIn any one contain fluorine atom.)

As the specific example of above-mentioned fluoroalkyl (c), can enumerate as the R in above-mentioned general formula (a-1)¹It illustrates Fluoroalkyl obtained from the end bonding oxygen atom of alkyl.

Fluoro-alkyl (a) in above-mentioned fluoro saturated cyclic carbonic ester, fluoro-alkyl (b) and fluoro with ehter bond The fluorine content of alkoxy (c) is preferably 10 mass % or more.If fluorine content is too low, enough reduction low temperature may not be able to be obtained Under viscosity effect, promoted flash-point effect.From this viewpoint, above-mentioned fluorine content is more preferably 12 mass % or more, into One step is preferably 15 mass % or more.The upper limit is generally 76 mass %.

The fluorine content of fluoro-alkyl (a), the fluoro-alkyl (b) with ehter bond and fluoroalkyl (c) is based on each group Structural formula, the value calculated according to { formula weight of (number × 19 of fluorine atom)/each group } × 100 (%).

In addition, from the viewpoint of dielectric constant, oxidative resistance are good, the fluorine of above-mentioned fluoro saturated cyclic carbonic ester entirety Content is preferably 10 mass % or more, more preferably 15 mass % or more.The upper limit is generally 76 mass %.

In addition, the fluorine content of above-mentioned fluoro saturated cyclic carbonic ester, be structural formula based on fluoro saturated cyclic carbonic ester, according to The value that { molecular weight of (number × 19 of fluorine atom)/fluoro saturated cyclic carbonic ester } × 100 (%) are calculated.

As above-mentioned fluoro saturated cyclic carbonic ester, specifically, such as following substance can be enumerated.

As X¹~X⁴In at least one be-F fluoro saturated cyclic carbonic ester specific example, can enumerate:

[changing 20]

Etc..

These compounds are high voltage withstanding, electrolytic salt dissolubility is also good.

In addition it can also be used:

[changing 21]

Deng.

As X¹~X⁴In at least one be fluoro-alkyl (a) and remaining all-H fluoro saturated cyclic carbonic acid The specific example of ester can be enumerated:

[changing 22]

[changing 23]

[changing 24]

Deng.

As X¹~X⁴In at least one be fluoro-alkyl (b) with ehter bond or fluoroalkyl (c) and remaining is complete Portion is the specific example of the fluoro saturated cyclic carbonic ester of-H, can be enumerated:

[changing 25]

[changing 26]

[changing 27]

[changing 28]

[changing 29]

[changing 30]

Deng.

Wherein, any one as above-mentioned fluoro saturated cyclic carbonic ester, in preferably following compound.

[changing 31]

[changing 32]

In addition, above-mentioned fluoro saturated cyclic carbonic ester is not limited only to above-mentioned specific example.In addition, above-mentioned fluoro saturation Cyclic carbonate can be used alone a kind, also can in any combination and ratio is used in combination of two or more.

As above-mentioned fluorinated chain carbonate, can enumerate by general formula (B):

Rf²OCOOR⁶ (B)

The compound of expression

(in formula, Rf²The fluoro-alkyl for being 1~7 for carbon atom number, R⁶The alkane containing fluorine atom for being 1~7 for carbon atom number Base.)

Rf²The fluoro-alkyl for being 1~7 for carbon atom number, R⁶The alkyl containing fluorine atom for being 1~7 for carbon atom number.

Above-mentioned fluoro-alkyl is group obtained from least one in hydrogen atom possessed by alkyl is replaced by fluorine atoms.Work as R⁶ When for alkyl containing fluorine atom, as fluoro-alkyl.

From less viscous viewpoint, Rf²And R⁶Carbon atom number be preferably 2~7, more preferably 2~4.

If carbon atom number excessively becomes larger, low-temperature characteristics may be reduced, and the dissolubility of electrolytic salt may reduce；If carbon is former Subnumber is very few, then it is possible that situations such as dissolubility of electrolytic salt reduces, discharging efficiency reduces, even viscosity increases.

The fluoro-alkyl for being 1 as carbon atom number, can enumerate CFH₂-、CF₂H- and CF₃-.Particularly, CF₂H- and CF₃It is preferred in terms of High temperature storage characteristic.

The fluoro-alkyl for being 2 or more as carbon atom number, from the viewpoint of the favorable solubility of electrolytic salt, preferably Enumerate the fluoro-alkyl indicated by the following general formula (d-1).

R¹-R²- (d-1)

R¹For that can have the alkyl that the carbon atom number of fluorine atom is 1 or more.As R¹, preferably carbon atom number be 1~6 it is straight The alkyl of chain or branched.As R¹Carbon atom number, more preferable 1~6, further preferred 1~3.

As R¹, specifically, as the alkyl of straight-chain or branched, CH can be enumerated₃-、CH₃CH₂-、CH₃CH₂CH₂-、 CH₃CH₂CH₂CH₂-、

[changing 33]

Deng.

In addition, working as R¹For the branched with fluorine atom alkyl when, it is preferable to enumerate:

[changing 34]

[changing 35]

Deng.

R²For that can have the alkylidene that the carbon atom number of fluorine atom is 1~3.R²It can be straight-chain, can also be branched 's.The example for constituting the minimum structural unit of alkylidene of such straight-chain or branched is illustrated below.R²Individually by them It constitutes or is made of their combination.

(i) minimum structural unit of straight-chain:

-CH₂-、-CHF-、-CF₂-、-CHCl-、-CFCl-、-CCl₂-。

(ii) minimum structural unit of branched:

[changing 36]

Work as R²When for straight-chain, R²It is only made of the minimum structural unit of above-mentioned straight-chain, wherein it is preferred that-CH₂-、- CH₂CH₂Or-CF₂-.From the viewpoint of capable of being made further to improve the dissolubility of electrolytic salt, more preferable-CH₂Or- CH₂CH₂-。

Work as R²When for branched, R²For the group of the minimum structural unit containing the above-mentioned branched of at least one, preferably It enumerates by general formula-(CX^aX^bGroup (the X for)-indicate^aFor H, F, CH₃Or CF₃；X^bFor CH₃Or CF₃.Wherein, work as X^bFor CF₃When, X^aFor H or CH₃).They especially can be such that the dissolubility of electrolytic salt further improves.

As preferred fluoro-alkyl, specifically, such as CF can be enumerated₃CF₂-、HCF₂CF₂-、H₂CFCF₂-、CH₃CF₂-、 CF₃CF₂CF₂-、HCF₂CF₂CF₂-、H₂CFCF₂CF₂-、CH₃CF₂CF₂-、

[changing 37]

[changing 38]

Deng.

Wherein, as Rf²And R⁶Fluoro-alkyl, preferably CF₃-、CF₃CF₂-、(CF₃)₂CH-、CF₃CH₂-、C₂F₅CH₂-、 CF₃CF₂CH₂-、HCF₂CF₂CH₂-、CF₃CFHCF₂CH₂, from anti-flammability is high, multiplying power property is good, the good viewpoint of oxidative resistance It sets out, more preferable CF₃CH₂-、CF₃CF₂CH₂-、HCF₂CF₂CH₂-。

R⁶It is the alkyl that carbon atom number is 1~7 for alkyl without fluorine atom.From less viscous viewpoint It sets out, R⁶Carbon atom number be preferably 1~4, more preferably 1~3.

As the above-mentioned alkyl without fluorine atom, such as CH can be enumerated₃-、CH₃CH₂-、(CH₃)₂CH-、C₃H₇Etc..Its In, multiplying power property low from the viewpoint of viscosity is good, preferably CH₃-、CH₃CH₂-。

The fluorine containing ratio of above-mentioned fluorinated chain carbonate is preferably 20~70 mass %.If fluorine containing ratio is above-mentioned model It encloses, then can maintain the dissolubility with the intermiscibility of solvent, salt.Above-mentioned fluorine containing ratio is more preferably 30 mass % or more, further Preferably 35 mass % or more, more preferably 60 mass % are hereinafter, further preferably 50 mass % or less.

In addition, the fluorine containing ratio in the present invention, be structural formula based on above-mentioned fluorinated chain carbonate, according to

{ molecular weight of (number × 19 of fluorine atom)/fluorinated chain carbonate } × 100 (%)

The value of calculating.

It is any one in compound preferably below from less viscous viewpoint as above-mentioned fluorinated chain carbonate It is a.

[changing 39]

Above-mentioned additive is selected from by additive (I), additive (II), additive (III), additive (IV) and addition At least one of the group of agent (V) composition.

Additive (I) has the structure indicated by following general formula (I).

[changing 40]

As additive (I), preferably by the compound of following general formula (10) expression.

[changing 41]

(in formula, R¹⁰¹~R¹⁰³Can be identical or different, be organic group).

It as above-mentioned organic group, can enumerate: the fluoroalkane that alkyl that carbon atom number is 1~10, carbon atom number are 1~10 Fluoroalkyl that alkoxy that base, carbon atom number are 1~10, carbon atom number are 1~10, by formula :-N (R¹⁰⁴)₂The base of expression It rolls into a ball, by formula :-Si (R¹⁰⁵)₃The group of expression, by formula :-OSi (R¹⁰⁶)₃The group of expression, by formula :-R¹⁰⁸-S-R¹⁰⁷, formula :-O- R¹⁰⁹Group that-CN is indicated, by formula: group etc. that-O-Li is indicated.

R¹⁰⁴~R¹⁰⁷For carbon atom number be 1~4 alkyl or carbon atom number be 1~4 fluoro-alkyl, R¹⁰⁸And R¹⁰⁹For carbon original The fluoro-alkyl that the alkylidene or carbon atom number that subnumber is 1~3 are 1~3.

As additive (I), can enumerate: (CH₃CH₂O)₃P=O, (CF₃CH₂O)₃P=O,

(CF₃CF₂CH₂O)₃P=O, (HCF₂CF₂CH₂O)₃P=O, (CH₃CH₂O)₂(CH₃CH₂) P=O, (CH₃CH₂)₂(CH₃O) P= O、[(CH₃)₂N]₃P=O, [(CH₃)₃Si](CH₃O)₂P=O,

[(CH₃)₃SiO]₃P=O, [(CH₃CH₂)]₂(CH₃CH₂SCH₂) P=O,

(CF₃CH₂O)₂(NCCH₂CH₂O) P=O, F₂(LiO) P=O, (LiO) (CF₃CH₂O)₂P=O, (LiO) (CH₃CH₂O)₂P= O、(LiO)(CH₃O)₂P=O etc..

Additive (II) is indicated by following general formula (II).

[changing 42]

As additive (II), following compound can be enumerated.

[changing 43]

[changing 44]

[changing 45]

[changing 46]

[changing 47]

[changing 48]

[changing 49]

[changing 50]

[changing 51]

Wherein, any one as additive (II), in preferably following compound.[changing 52]

Additive (III) is indicated by following general formula (III).[changing 53]

As additive (III), following compound can be enumerated.

[changing 54]

[changing 55]

[changing 56]

[changing 57]

[changing 58]

[changing 59]

[changing 60]

[changing 61]

[changing 62]

Wherein, any one as additive (III), in preferably following compound.

[changing 63]

Additive (IV) has the structure indicated by any one in following general formula (IV).- C ≡ N ,-N=C=O,

[changing 64]

[changing 65]

[changing 66]

As additive (IV), it is preferably selected from the group being made of compound (5)~(9), (11) and (12) extremely It is a kind few.

Compound (5) is indicated by following general formula (5).

NC-R⁵¹-(CN)_n51

(in formula, R⁵¹For the alkyl of 1~trivalent or halohydrocarbyl, the n of 1~trivalent⁵¹Integer for 0~2).

As above-mentioned alkyl or above-mentioned halohydrocarbyl, can enumerate the alkyl, carbon atom number that carbon atom number is 1~10 be 3~ Cycloalkylidene that alkylidene that 10 naphthenic base, carbon atom number are 1~10, carbon atom number are 3~10, carbon atom number are 1~10 Alkylidene, the secondary naphthenic base etc. that carbon atom number is 3~10.Above-mentioned alkyl can contain-S (=O)₂,-S (=O)₂- O- ,-P= O。

As above-mentioned naphthenic base, cyclohexyl etc. can be enumerated.In the hydrogen atom of above-mentioned naphthenic base part or all can by- S (=O)₂,-S (=O)₂- O- ,-P=O or-OM⁵²(M⁵²For metallic atom) etc. replace.

As above-mentioned secondary naphthenic base, hexylidyne etc. can be enumerated.In the hydrogen atom of above-mentioned secondary naphthenic base part or all can by- S (=O)₂,-S (=O)₂- O- ,-P=O or-OM⁵²(M⁵²For metallic atom) etc. replace.

As compound (5), it is preferably selected from by the expression of following general formula (5-1), general formula (5-2) and general formula (5-3) Compound group that is at least one kind of in the group of compound composition, more preferably being indicated by following general formula (5-2) and general formula (5-3) At group in it is at least one kind of.

General formula (5-1):

R⁵²-CN。

(in formula, R⁵²For carbon atom number be 1~10 alkyl or formula :-R⁵³-CN(R⁵³For the alkylene of carbon atom number 1~10 Base).)

General formula (5-2):

NC-R⁵⁴-CN。

(in formula, R⁵⁴For the alkylidene of carbon atom number 1~10)

General formula (5-3):

[changing 67]

(in formula, R⁵⁵The secondary naphthenic base that alkylidene or carbon atom number for carbon atom number 1~10 are 3~10.)

As compound (5), can enumerate: acetonitrile, propionitrile, butyronitrile, succinonitrile, glutaronitrile, adiponitrile, octafluoro adiponitrile, Penta trimethylsilyl nitrile of 1,3,5-, three nitrile of 1,3,6- hexane, three nitrile of 1,3,5- hexamethylene, CH₃SO₃C₂H₅CN etc..Among them, preferably have The compound of multiple CN bases.

Compound (6) is indicated by following general formula (6).

OCN-R⁶¹-(NCO)_n61。

(in formula, R⁶¹For the halohydrocarbyl of the alkyl or 1 valence or divalent of 1 valence or divalent, n⁶¹It is 0 or 1.)

As above-mentioned alkyl or above-mentioned halohydrocarbyl, can enumerate the alkyl, carbon atom number that carbon atom number is 1~10 be 1~ Alkylidene that naphthenic base that 10 halogenated alkyl, carbon atom number are 3~10, carbon atom number are 1~10, carbon atom number are 1~10 Halogeno alkylen, the cycloalkylidene etc. that carbon atom number is 3~10.

As compound (6), the compound represented by being preferably selected from by following general formula (6-1) and general formula (6-2) is formed Group in it is at least one kind of.

General formula (6-1):

R⁶²-NCO

(in formula, R⁶²There can be the alkyl that the carbon atom number of cyclic structure is 1~10, or there can be the carbon of cyclic structure former The halogenated alkyl that subnumber is 1~10.)

General formula (6-2):

OCN-R⁶³-NCO

(in formula, R⁶³There can be the alkylidene that the carbon atom number of cyclic structure is 1~10, or there can be the carbon of cyclic structure The halogeno alkylen that atomicity is 1~10)

As compound (6), hexamethylene diisocyanate, 1,3- bis- (isocyanatomethyl) hexamethylene can be enumerated Deng.

Compound (7) is indicated by following general formula (7).

[changing 68]

(in formula, R⁷¹And R⁷²Can be identical or different, it is the halogenated of halogen atom, the alkyl of 1 valence or divalent or 1 valence or divalent Alkyl, R⁷¹And R⁷²It can also formation ring bonding to each other.)

As above-mentioned alkyl or above-mentioned halohydrocarbyl, can enumerate: alkyl that carbon atom number is 1~10, carbon atom number be 1~ Fluoroalkyl that alkoxy that 10 fluoro-alkyl, carbon atom number are 1~10, carbon atom number are 1~10, carbon atom number 1 Fluoro oxygroup alkylidene that fluorianted alkylene that~10 alkylidene, carbon atom number are 1~10, carbon atom number are 1~10, carbon are former The fluoro alkenylene etc. that alkenylene that subnumber is 2~10, carbon atom number are 2~10.There can be ether when carbon atom number is 2 or more Key.

As compound (7), preferably by the compound of following general formula (7-1) expression.

[changing 69]

(in formula, R⁷³For the alkylidene of carbon atom number 2 or 3 or the fluorianted alkylene of carbon atom number 2 or 3.)

Compound (8) is indicated by following general formula (8).

[changing 70]

(in formula, R⁸¹And R⁸²Can be identical or different, it is the halogenated of halogen atom, the alkyl of 1 valence or divalent or 1 valence or divalent Alkyl, R⁸¹And R⁸²It can formation ring bonding to each other.)

As above-mentioned alkyl or above-mentioned halohydrocarbyl, can enumerate: alkyl that carbon atom number is 1~10, carbon atom number be 1~ Fluoroalkyl that alkoxy that 10 fluoro-alkyl, carbon atom number are 1~10, carbon atom number are 1~10, carbon atom number 1 The fluoro oxygroup alkylidene etc. that fluorianted alkylene that~10 alkylidene, carbon atom number are 1~10, carbon atom number are 1~10.When When carbon atom number is 2 or more, there can be ehter bond, unsaturated bond can also be contained.

As compound (8), it is preferably selected from by following general formula (8-1) compound indicated and by general formula (8-2) table It is at least one kind of in group composed by the compound shown.

General formula (8-1):

[changing 71]

(in formula, n⁸¹It is 0 or 1, n⁸²It is 0 or 1, R⁸³For the carbon atom number containing unsaturated bond be 2~6 alkylidene or can The fluorianted alkylene that carbon atom number containing unsaturated bond is 2~6.)

General formula (8-2):

[changing 72]

(in formula, R⁸⁴For F, carbon atom number be 1~5 alkyl or carbon atom number be 1~5 fluoro-alkyl, R⁸⁵For F, carbon atom The fluoro-alkyl that the alkyl or carbon atom number that number is 1~5 are 1~5.)

Compound (9) is indicated by following general formula (9).

[changing 73]

(in formula, R⁹¹And R⁹²Can be identical or different, it is the halogenated of halogen atom, the alkyl of 1 valence or divalent or 1 valence or divalent Alkyl, R⁹¹And R⁹²Can formation ring bonding to each other, the alkylidene that Z is oxygen atom or carbon atom number is 1~10)

As above-mentioned alkyl or above-mentioned halohydrocarbyl, can enumerate the alkyl, carbon atom number that carbon atom number is 1~10 be 1~ Fluoroalkyl that alkoxy that 10 fluoro-alkyl, carbon atom number are 1~10, carbon atom number are 1~10, carbon atom number 1 The fluoro oxygroup alkylidene etc. that fluorianted alkylene that~10 alkylidene, carbon atom number are 1~10, carbon atom number are 1~10.When Carbon atom number can have ehter bond when being 2 or more.

Compound and following general formula (9- as compound (9), represented by being preferably selected from by following general formula (9-1) 2) at least one kind of in the group of the compound composition represented by.

General formula (9-1):

[changing 74]

(in formula, R⁹³And R⁹⁴Can be identical or different, it is the alkylidene of carbon atom number 1~3.)

General formula (9-2):

[changing 75]

(in formula, R⁹⁵And R⁹⁶Can be identical or different, be the alkyl of carbon atom number 1~3)

As compound (7)~(9), can enumerate in 1,3-propane sultone, 2,4- butane sultone, Isosorbide-5-Nitrae-butane sulphur Ester, 1,3- propene sultone, methane sulfonic acid acid anhydride, methane sulfonic acid propyl ester, methane sulfonic acid tetrafluoro propyl ester, dimethyl sulfoxide, ring fourth Sulfone, glycol sulfite, ethyl sulfate, methane-disulfonic acid methylene ester, 3- fluorine sulfolane, the fluoro- 1,3- propane sultone of 3-, list Fluorine-based ethyl sulfate etc..

Compound (11) is indicated by following general formula (11).

[changing 76]

(in formula, R¹¹¹~R¹¹⁶It is identical or different, it is halogen atom or organic group.)

As halogen atom, preferably F.It as organic group, can enumerate: the alkoxies such as methoxyl group, ethyoxyl, phenoxy group, first The aryloxy group such as phenoxyl, the alkyl such as methyl, ethyl, the aryl such as phenyl, tolyl, the substituted types amino such as including methylamino Amino, the alkylthio groups such as methyl mercapto, ethylmercapto group, the arylthios such as thiophenyl.

As compound (11), three phosphonitrile of hexafluoro ring, five fluorine (phenoxy group) ring, three phosphonitrile, ethyoxyl (five fluorine) ring can be enumerated Three phosphonitriles, three phosphonitrile of ethyoxyl (seven fluorine) ring etc..

Compound (12) is indicated by following general formula (12).

[changing 77]

(in formula, R¹²¹~R¹²⁸Can be identical or different, it is halogen atom or organic group.)

As compound (12), four phosphonitrile of ethyoxyl (five fluorine) ring can be enumerated.

Additive (V) is indicated by following general formula (V).

[changing 78]

(in formula, A^a+For metal ion, hydrogen ion or ion.The integer that a is 1~3, the integer that b is 1~3, p b/a, n²³ For 1~4 integer, n²¹For 0~8 integer, n²²It is 0 or 1, Z²¹For transition metal, the III-th family of the periodic table of elements, Group IV Or the element of group V.

X²¹For O, S, carbon atom number be 1~10 alkylidene, carbon atom number be 1~10 halogeno alkylen, carbon atom number 6 Halogenated arlydene (alkylidene, halogeno alkylen, the arlydene and halogenated that~20 arlydene or carbon atom number is 6~20 Arlydene can have substituent group, hetero atom in its structure, or in n²²For 1 and n²³N when being 2~4²³A X²¹Key can be distinguished It closes).

L²¹For halogen atom, cyano, carbon atom number be 1~10 alkyl, carbon atom number be 1~10 halogenated alkyl, carbon atom number For 6~20 aryl, carbon atom number be 6~20 halogenated aryl (alkylidene, halogeno alkylen, arlydene and halogenated sub- virtue Base can have substituent group, hetero atom in its structure, or in n²¹N when being 2~8²¹A L²¹Ring can be bonded together to form respectively) or- Z²³Y²³。

Y²¹、Y²²And Z²³It is independently of one another O, S, NY²⁴, alkyl or fluoro alkyl.Y²³And Y²⁴Be independently of one another H, F, The aryl or carbon that halogenated alkyl that alkyl that carbon atom number is 1~10, carbon atom number are 1~10, carbon atom number are 6~20 are former (alkyl, halogenated alkyl, aryl and halogenated aryl can have substituent group, miscellaneous to the halogenated aryl that subnumber is 6~20 in its structure Atom works as Y²³Or Y²⁴There are it is multiple when can bond together to form ring).)

As A^a+, can enumerate: lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, barium ions, cesium ion, silver from Son, zinc ion, copper ion, cobalt ions, iron ion, nickel ion, manganese ion, titanium ion, lead ion, chromium ion, vanadium ion, ruthenium from Son, ruthenium ion, lanthanide ion, actinide ion, potassium ion, tetraethyl ammonium ion, tetramethyl ammonium, triethyl methyl Ammonium ion, triethyl ammonium ion, pyridinium ion, imidazol ion, hydrogen ion, tetraethylphosphonium ion, tetramethyl phosphonium ion, tetraphenyl Phosphonium ion, triphenylsulfonium ion, triethyl group sulfonium cation etc..

In purposes such as devices for electrochemistry, A^a+Preferably lithium ion, sodium ion, magnesium ion, tetraalkyl ammonium ion, Hydrogen ion, particularly preferably lithium ion.A^a+The integer that the chemical valence a of cation is 1~3.When being greater than 3, since lattice energy increases Greatly, therefore it will appear and become difficult to be dissolved in solvent such problems.Thus when needing solubility more preferable 1.Anion Chemical valence b is similarly 1~3 integer, particularly preferred 1.Indicate that the constant p of the ratio between cation and anion is inevitable by the two The ratio between chemical valence b/a is determined.

In the following, the ligand moiety of mutual-through type (V) is illustrated.In the present specification, with the Z in logical formula (V)²¹Bonding has Machine or inorganic part are known as ligand.

Z²¹Preferably Al, B, V, Ti, Si, Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf or Sb, more Preferably Al, B or P.

X²¹Indicate the halogeno alkylen, carbon atom that alkylidene, carbon atom number that O, S, carbon atom number are 1~10 are 1~10 The halogenated arlydene that the arlydene or carbon atom number that number is 6~20 are 6~20.These alkylidenes and arlydene can be in its knots There is substituent group, hetero atom in structure.Specifically, can have halogen atom, chain or cricoid alkyl, aryl, alkene as substituent group Base, alkoxy, aryloxy group, sulfonyl, amino, cyano, carbonyl, acyl group, amide groups, hydroxyl, to replace alkylidene and sub- virtue Hydrogen on base；It can also be the structure for being imported with nitrogen, sulphur, oxygen to replace the carbon on alkylidene and arlydene.In addition, working as n²²It is 1 And n²³When being 2~4, n²³A X²¹It can bond together.As such example, ligand as ethylenediamine tetra-acetic acid can be enumerated.

L²¹Indicate the halogenated alkyl, carbon that alkyl, carbon atom number that halogen atom, cyano, carbon atom number are 1~10 are 1~10 The halogenated aryl or-Z that aryl that atomicity is 6~20, carbon atom number are 6~20²³Y²³(about Z²³、Y²³, behind describe).This The alkyl and aryl and X at place²¹Can similarly have substituent group, hetero atom in its structure, in addition, working as n²¹N when being 2~8²¹ A L²¹It can bond together to form ring.As L²¹, preferably fluorine atom or cyano.For fluorine atom, anionic compound The solubility of salt, degree of dissociation improve, ionic conductivity increases accordingly.In addition, oxidative resistance improves, thus, it is possible to inhibit secondary anti- The generation answered.

Y²¹、Y²²And Z²³O, S, NY are indicated independently of one another²⁴, alkyl or fluoro alkyl.Y²¹And Y²²Preferably O, S, Or NY²⁴, more preferably O.As the feature of compound (V), due to having with internal based on Y same²¹And Y²²And Z²¹'s Key, these ligands and Z²¹Constitute chelate structure.Effect based on the chelating, it is the heat resistance of the compound, chemical stability, water-fast Solution property improves.Constant n in the ligand²²It is 0 or 1, but particularly, in n²²In the case where 0, since the chelate ring is five Member ring, therefore chelate effect is most played by force, stability increases, thus be preferred.

In addition, in the present specification, obtained from fluoro alkyl refers to that at least one in the hydrogen atom of alkyl is replaced by fluorine atoms Group.

Y²³And Y²⁴Be independently of one another H, F, carbon atom number be 1~10 alkyl, carbon atom number be 1~10 it is halogenated The halogenated aryl that the aryl or carbon atom number that alkyl, carbon atom number are 6~20 are 6~20, these alkyl and aryl can be at them There is substituent group or hetero atom, in addition, working as Y in structure²³Or Y²⁴There are it is multiple when, can be bonded to each other to form ring.

In addition, constant n relevant to the quantity of above-mentioned ligand²³For 1~4 integer, preferably 1 or 2, more preferably 2. In addition, constant n relevant to the quantity of above-mentioned ligand²¹For 0~8 integer, preferably 0~4 integer, more preferably 0,2, Or 4.Further, it is preferable to work as n²³N when being 1²¹It is 2, works as n²³N when being 2²¹It is 0.

In logical formula (V), alkyl, halogenated alkyl, aryl, halogenated aryl further include with branch, hydroxyl, ehter bond etc. other The group of functional group.

As compound (V), preferably following compound.

By general formula:

[changing 79]

Expression compound (in formula, A^a+、a、b、p、n²¹、Z²¹And L²¹It is same as described above)；Or

By general formula:

[changing 80]

Expression compound (in formula, A^a+、a、b、p、n²¹、Z²¹And L²¹It is same as described above)

As compound (V), Lithium bis (oxalate) borate salt can be enumerated；It can enumerate:

By following formula:

[changing 81]

The dioxalic acid lithium borate of expression,

By following formula:

[changing 82]

The difluorine oxalic acid boracic acid lithium of expression and by following formula:

[changing 83]

Dicyano Lithium bis (oxalate) borate of expression etc..

As compound (V), can also enumerate: by following formula:

[changing 84]

The tetrafluoro oxalic acid lithium phosphate of expression and by following formula:

[changing 85]

The difluoro of expression bis- (oxalates) closes lithium phosphate etc..

Above-mentioned additive is selected from being made of additive (I), additive (III), additive (IV) and additive (V) The electrolyte of at least one of group be also one of preferred mode of the invention.According to which, have the effect that i.e. Make to store at high temperature, compared with immediately after preparation, residual capacity is not easy to reduce, and resistance increment rate is also not easy to change.

The electrolyte that above-mentioned fluoro carbonic ester is fluorinated chain carbonate, above-mentioned additive is additive (II) is also this hair One of bright preferred mode.According to which, has the effect that even if storing at high temperature, compared with immediately after preparation, remain Covolume amount is not easy to reduce, and resistance increment rate is also not easy to change.

Above-mentioned electrolyte preferably contains relative to above-mentioned electrolyte:

The compound (1) of 0.0001~95 mass %,

The above-mentioned fluoro carbonic ester of 0.0001~95 mass % and

The above-mentioned additive of 0.00001~15 mass %.

Above-mentioned electrolyte more preferably contains relative to above-mentioned electrolyte:

The compound (1) of 5~85 mass %,

The above-mentioned fluoro carbonic ester of 5~85 mass % and

The above-mentioned additive of 0.01~10 mass %.

Above-mentioned electrolyte further preferably contains relative to above-mentioned electrolyte:

The compound (1) of 24.9~75 mass %,

The above-mentioned fluoro carbonic ester of 24.9~75 mass % and

The above-mentioned additive of 0.1~3 mass %.

When use above-mentioned fluoro saturated cyclic carbonic ester and above-mentioned fluorinated chain carbonate as above-mentioned fluoro carbonic ester When, above-mentioned fluoro saturated cyclic carbonic ester and above-mentioned fluorinated chain carbonate ratio (above-mentioned fluoro saturated cyclic carbonic ester/on State fluorinated chain carbonate) it is preferably 10/90~90/10.

Above-mentioned electrolyte can further contain the carbonic ester of non-fluoro.As the carbonic ester of above-mentioned non-fluoro, can enumerate not The saturated cyclic carbonic ester of fluoro, linear carbonate of non-fluoro etc..

As the saturated cyclic carbonic ester of above-mentioned non-fluoro, such as ethylene carbonate (EC), propylene carbonate can be enumerated (PC), butylene carbonate etc..

Wherein, the saturated cyclic carbonic ester as above-mentioned non-fluoro, from the viewpoint of dielectric constant, high, viscosity is suitable for, At least one kind of compound being preferably selected from the group being made of ethylene carbonate, propylene carbonate and butylene carbonate.

As the saturated cyclic carbonic ester of above-mentioned non-fluoro, a kind in above compound can be used, can also and with 2 kinds therein More than.

As the linear carbonate of above-mentioned non-fluoro, such as CH can be enumerated₃OCOOCH₃(dimethyl carbonate: DMC), CH₃CH₂OCOOCH₂CH₃(diethyl carbonate: DEC), CH₃CH₂OCOOCH₃(methyl ethyl carbonate: EMC), CH₃OCOOCH₂CH₂CH₃ The hydro carbons linear carbonate such as (methyl propyl carbonate), carbonic acid first butyl ester, ethyl propyl carbonic acid ester, ethyl butyl carbonate.Wherein, be preferably selected from by It is at least one kind of in the group of methyl ethyl carbonate, diethyl carbonate and dimethyl carbonate composition.

In order not to damage the performance of above-mentioned electrolyte, the content of the linear carbonate as above-mentioned non-fluoro, relative to upper Electrolyte preferably 25 mass % or less, more preferable 10 mass % are stated hereinafter, lower limit can be 0 mass %.

Among electrolyte of the invention, the electrolyte containing the compound (1) for being 0 of the n11 in general formula (1) be it is preferred, Because its residual capacity before and after High temperature storage is big, resistance increment rate is small.

That is, the feature of the electrolyte of one of preferred mode of the invention is to contain:

By general formula (1-1): R¹¹CFX¹¹COOR¹²Expression compound (1-1) (in formula, R¹¹It is 1~3 for H, F, carbon atom number The fluoro-alkyl that non-fluoro-alkyl or carbon atom number are 1~3, X¹¹For H or F, R¹²The non-fluoro for being 1~3 for carbon atom number The fluoro-alkyl that alkyl or carbon atom number are 1~3)；

Fluoro carbonic ester；And

Selected from represented by the additive (I) represented by leading to formula (I), additive (II), logical formula (III) represented by logical formula (II) Additive (III), the additive (IV) with structure represented by any one in logical formula (IV) and logical formula (V) institute At least one kind of additive in the group of additive (V) composition of expression.

(in the present specification, above-mentioned electrolyte is also referred to as " electrolyte (1) ".)

According to electrolyte (1), the problem of electrolyte as described below is provided can solve: and rigid even if storing at high temperature It is compared after preparation, residual capacity is not easy to reduce, resistance increment rate is also not easy to change, moreover, before and after High temperature storage, residual capacity is equal Greatly, resistance increment rate is small.

Among electrolyte (1), preferably above-mentioned additive is selected from by additive (I), additive (III), additive (IV) at least one kind of and in the group of additive (V) composition.In addition, above-mentioned additive be selected from by additive (I), At least one of additive (II), additive (III) and group of additive (IV) composition, more preferably selected from by adding At least one of agent (I), additive (II) and group of additive (III) composition, further preferably selected from by additive (I) and at least one of the group of additive (III) composition.

In addition, in electrolyte (1), it is also preferred that above-mentioned fluoro carbonic ester is fluorinated chain carbonate, above-mentioned additive is Additive (II).

As compound (1-1), it is preferably selected from by CHF₂COOCH₃、CF₃CHFCOOCH₃、CHF₂COOC₂H₅、 CHF₂CF₂COOC₂H₅、CF₃CHFCOOCH₃、CF₃CHFCOOC₂H₅、CH₃CF₂COOCH₃、CH₃CF₂COOC₂H₅In the group of composition extremely It is a kind few.

Suitable component in other electrolyte (1) etc. is identical as component contained by electrolyte of the invention etc..

Electrolyte (1) contains preferably with respect to electrolyte (1):

The compound (1-1) of 0.0001~95 mass %,

The above-mentioned fluoro carbonic ester of 0.0001~95 mass % and

The above-mentioned additive of 0.00001~15 mass %.

Electrolyte (1) more preferably contains relative to electrolyte (1):

The compound (1-1) of 5~85 mass %,

The above-mentioned fluoro carbonic ester of 5~85 mass % and

The above-mentioned additive of 0.01~10 mass %.

The compound (1) of 24.9~75 mass %,

The above-mentioned fluoro carbonic ester of 24.9~75 mass % and

The above-mentioned additive of 0.1~3 mass %.

When use above-mentioned fluoro saturated cyclic carbonic ester and above-mentioned fluorinated chain carbonate as above-mentioned fluoro carbonic ester When, ratio (the above-mentioned fluoro saturated cyclic carbonic acid as above-mentioned fluoro saturated cyclic carbonic ester and above-mentioned fluorinated chain carbonate Ester/above-mentioned fluorinated chain carbonate) preferably 10/90~90/10.

As described above, electrolyte of the invention contains the carbonic ester of above-mentioned non-fluoro.Particularly, from above-mentioned fluorine can be cut down From the perspective of the usage amount of carbonic ester, the electrolysis of the saturated cyclic carbonic ester of the above-mentioned non-fluoro containing 5~30 mass % Liquid has although performance is sometimes slightly insufficient and is enough to make up the insufficient advantage economically.

By general formula (1): R¹¹CFX¹¹(CH₂)_n11COOR¹²Expression compound (1) (in formula, R¹¹It is 1~3 for H, F, carbon atom number Non- fluoro-alkyl or carbon atom number be 1~3 fluoro-alkyl, X¹¹For H or F, R¹²The non-fluorine for being 1~3 for carbon atom number The fluoro-alkyl that substituted alkyl or carbon atom number are 1~3, the integer that n11 is 0~3)；

Fluoro carbonic ester；

Selected from represented by the additive (I) represented by leading to formula (I), additive (II), logical formula (III) represented by logical formula (II) Additive (III), the additive (IV) with structure represented by any one in logical formula (IV) and logical formula (V) institute At least one kind of additive in the group of additive (V) composition of expression；And

The saturated cyclic carbonic ester of the non-fluoro of 0.01~40 mass %.

(in the present specification, above-mentioned electrolyte is also referred to as " electrolyte (2) ".)

According to electrolyte (2), the problem of electrolyte as described below is provided can solve: and rigid even if storing at high temperature It is compared after preparation, residual capacity is also not easy to reduce, resistance increment rate is also not easy to change；Moreover, price competitiveness is excellent.

The content of the saturated cyclic carbonic ester of above-mentioned non-fluoro is preferably 10 mass % or more relative to above-mentioned electrolyte.If The saturated cyclic carbonic ester of above-mentioned non-fluoro is excessive, then may cannot get desired performance.

In electrolyte (2), above-mentioned additive be preferably selected from by additive (I), additive (III), additive (IV), And it is at least one kind of in the group of additive (V) composition.

In addition, above-mentioned fluoro carbonic ester is fluorinated chain carbonate, above-mentioned additive is additive in electrolyte (2) (II) the case where is also preferred.

Suitable component in other electrolyte (2) etc. is identical as component contained by electrolyte of the invention etc..

Electrolyte (2) contains preferably with respect to electrolyte (2):

The compound (1) of 0.0001~95 mass %,

The above-mentioned fluoro carbonic ester of 0.0001~95 mass %,

The above-mentioned additive of 0.00001~15 mass % and

The saturated cyclic carbonic ester of the above-mentioned non-fluoro of 0.0001~40 mass %.

Electrolyte (2) more preferably contains relative to electrolyte (2):

The compound (1) of 10~75 mass %,

The above-mentioned fluoro carbonic ester of 5~75 mass %,

The above-mentioned additive of 0.01~10 mass % and

The saturated cyclic carbonic ester of the above-mentioned non-fluoro of 1~30 mass %.

Electrolyte (2) further preferably contains relative to electrolyte (2):

The compound (1) of 15~65 mass %,

The above-mentioned fluoro carbonic ester of 15~75 mass %,

The above-mentioned additive of 0.5~3 mass % and

The saturated cyclic carbonic ester of the above-mentioned non-fluoro of 1~20 mass %.

From the viewpoint of oxidative resistance is excellent, among electrolyte of the invention, the electrolyte that is preferably as described below:

The compound (1) for being 1 or 2 containing the n11 in general formula (1)；

Moreover, containing by general formula (3): R³¹R³²R³³C-OCOO-CR³⁴R³⁵Rf³¹The fluoro carbonic ester of expression is as above-mentioned fluoro carbon Acid esters (in formula, R³¹~R³⁵It is identical or different, it is-H ,-CH₃Or-CF₃；R³¹~R³³In one and R³⁴~R³⁵In one can Respectively singly-bound forms ring by the two bonding；Rf³¹For fluoro-alkyl).

That is, the electrolyte of one of preferred mode of the invention, feature is to contain:

By general formula (1-2): R¹¹CFX¹¹(CH₂)_n11COOR¹²Expression compound (1-2) (in formula, R¹¹For H, F, carbon atom number 1 The fluoro-alkyl that~3 non-fluoro-alkyl or carbon atom number is 1~3, X¹¹For H or F, R¹²For the non-fluorine of carbon atom number 1~3 The fluoro-alkyl of substituted alkyl or carbon atom number 1~3, n11 are 1 or 2)；

By general formula (3): R³¹R³²R³³C-OCOO-CR³⁴R³⁵Rf³¹Expression fluoro carbonic ester (3) (in formula, R³¹~R³⁵It is identical or not It together, is-H ,-CH₃Or-CF₃, R³¹~R³³In one and R³⁴~R³⁵In one may respectively be singly-bound, by the two bonding come Form ring.Rf³¹For fluoro-alkyl)；And

Selected from represented by the additive (I) represented by leading to formula (I), additive (II), logical formula (III) represented by logical formula (II) Additive (III), the additive (IV) with structure represented by any of logical formula (IV) and logical formula (V) institute table At least one kind of additive in the group of additive (V) composition shown.

(in the present specification, above-mentioned electrolyte is also referred to as " electrolyte (3) ".)

According to electrolyte (3), the problem of electrolyte as described below is provided can solve: and rigid even if storing at high temperature It is compared after preparation, residual capacity is also not easy to reduce, and resistance increment rate is also not easy to change；Moreover, oxidative resistance is excellent.

In electrolyte (3), above-mentioned additive be preferably selected from by additive (I), additive (III), additive (IV), And it is at least one kind of in the group of additive (V) composition.

Fluoro carbonic ester (3) can be fluoro saturated cyclic carbonic ester, can also be fluorinated chain carbonate.In addition, also excellent It is selected in that fluoro carbonic ester (3) in electrolyte (3) is fluorinated chain carbonate, above-mentioned additive is additive (II).

As compound (1-2), it is preferably selected from by CF₃CH₂COOCH₃And CF₃CH₂CH₂COOCH₃In the group of composition It is at least one kind of.

In general formula (3), as Rf³¹, preferably carbon atom number is 1~3 fluoro-alkyl, more preferably-CF₃、-CHCF₃、 Or-CF₂H。

As fluoro carbonic ester (3), particularly preferred following compound.

[changing 86]

Suitable component in other electrolyte (3) etc. is identical as component contained by electrolyte of the invention etc..

Electrolyte (3) contains preferably with respect to electrolyte (3):

The compound (1-2) of 0.0001~95 mass %,

The fluoro carbonic ester (3) of 0.0001~95 mass % and

The above-mentioned additive of 0.00001~15 mass %.

Electrolyte (3) more preferably contains relative to electrolyte (3):

The compound (1-2) of 5~85 mass %,

The fluoro carbonic ester (3) of 5~85 mass % and

The above-mentioned additive of 0.01~10 mass %.

Electrolyte (3) further preferably contains relative to electrolyte (3):

The compound (1-2) of 24.5~75 mass %,

The fluoro carbonic ester (3) of 24.5~75 mass % and

The above-mentioned additive of 0.5~3 mass %.

When use above-mentioned fluoro saturated cyclic carbonic ester and above-mentioned fluorinated chain carbonate as fluoro carbonic ester (3) When, ratio (the above-mentioned fluoro saturated cyclic carbonic acid as above-mentioned fluoro saturated cyclic carbonic ester and above-mentioned fluorinated chain carbonate Ester/above-mentioned fluorinated chain carbonate) preferably 10/90~90/10.

Electrolyte of the invention preferably comprises electrolytic salt (except additive (I) and additive (V)).

May be used also in addition to alkali metal salt, alkali salt, aluminium are as cationic metal salt, ammonium salt as above-mentioned electrolytic salt It can be used for electrolyte using liquid salt (ionic liquid), the salt of inorganic polymer type, salt of organic polymer type etc. Arbitrary electrolytic salt.

As the electrolytic salt of electrolyte solution for lithium ion secondary battery, preferred as alkali salt, more preferable lithium salts.

It as above-mentioned lithium salts, such as can enumerate: LiClO₄、LiPF₆、LiBF₄Equal inorganic lithium salts；LiCF₃SO₃、LiN(CF₃SO₂)₂、 LiN(C₂F₅SO₂)₂、LiN(CF₃SO₂)(C₄F₉SO₂)、LiC(CF₃SO₂)₃、LiPF₄(CF₃)₂、LiPF₄(C₂F₅)₂、LiPF₄ (CF₃SO₂)₂、LiPF₄(C₂F₅SO₂)₂、LiBF₂(CF₃)₂、LiBF₂(C₂F₅)₂、LiBF₂(CF₃SO₂)₂、LiBF₂(C₂F₅SO₂)₂, by Formula: LiPF_a(C_nF_2n+1)_6-aThe fluorine-containing organic acid lithium salts such as the salt (in formula, integer that integer that a is 0~5, n are 1~6) of expression Deng.They may be used alone or in combination two or more use.

Wherein, from the viewpoint of the deterioration after it can inhibit electrolyte High temperature storage, above-mentioned lithium salts be preferably selected from by LiPF₆、LiBF₄、LiCF₃SO₃、LiN(CF₃SO₂)₂、LiN(C₂F₅SO₂)₂And by formula: LiPF_a(C_nF_2n+1)_6-aThe salt of expression It is at least one kind of in the group of (in formula, integer that integer that a is 0~5, n are 1~6) composition.

As by formula: LiPF_a(C_nF_2n+1)_6-aThe salt of expression, such as can enumerate: LiPF₃(CF₃)₃、LiPF₃(C₂F₅)₃、 LiPF₃(C₃F₇)₃、LiPF₃(C₄F₉)₃、LiPF₄(CF₃)₂、LiPF₄(C₂F₅)₂、LiPF₄(C₃F₇)₂、LiPF₄(C₄F₉)₂Deng.(wherein, In formula by C₃F₇、C₄F₉The alkyl of expression can be any one in straight chain, branched structure.)

The concentration of above-mentioned lithium salts in electrolyte is preferably 0.5~3 mol/L.If outside the range, the electricity of electrolyte Conductance reduces, and battery performance has the tendency that reduction.

The concentration of above-mentioned electrolytic salt is more preferably 0.9 mol/L or more, below more preferably 1.5 mol/Ls.

As the electrolytic salt of electrolyte solution for electric double layer capacitor, preferably ammonium salt.

As above-mentioned ammonium salt, following (IIa)~(IIe) can be enumerated.

(IIa) tetraalkyl ammonium salt

Preferably enumerate the tetraalkyl ammonium salt indicated by following general formula (IIa):

[changing 87]

(in formula, R^1a、R^2a、R^3aAnd R^4aIt is identical or different, it is the alkyl containing ehter bond that carbon atom number is 1~6；X^- For anion).

In addition, part or all of the hydrogen atom of the ammonium salt is taken by the fluoro-alkyl that fluorine atom and/or carbon atom number are 1~4 The compound in generation is preferred from the viewpoint of oxidative resistance raising.

As concrete example, the tetraalkyl ammonium salt indicated by general formula (IIa-1) can be enumerated, by general formula (IIa-2) expression Trialkyl ammonium salts etc. containing alkylether radicals:

[changing 88]

(in formula, R^1a、R^2aAnd X^-As hereinbefore；X and y are identical or different, are 0~4 integer, and x+y=4.)

[changing 89]

(in formula, R^5aThe alkyl for being 1~6 for carbon atom number；R^6aThe divalent alkyl for being 1~6 for carbon atom number；R^7aFor carbon atom number For 1~4 alkyl；Z is 1 or 2；X^-For anion.)

By importing alkylether radicals, the reduction of viscosity can be expected.

Anion X^-It can be inorganic anion, can also be organic anion.As inorganic anion, such as can enumerate AlCl₄ ^-、BF₄ ^-、PF₆ ^-、AsF₆ ^-、TaF₆ ^-、I^-、SbF₆ ^-.As organic anion, such as CF can be enumerated₃COO^-、CF₃SO₃ ^-、 (CF₃SO₂)₂N^-、(C₂F₅SO₂)₂N^-Deng.

Among them, from the viewpoint of oxidative resistance, ionic dissociation are good, preferably BF₄ ^-、PF₆ ^-、AsF₆ ^-、SbF₆ ^-。

As the suitable specific example of tetraalkyl ammonium salt, Et can be used₄NBF₄、Et₄NClO₄、Et₄NPF₆、 Et₄NAsF₆、Et₄NSbF₆、Et₄NCF₃SO₃、Et₄N(CF₃SO₂)₂N、Et₄NC₄F₉SO₃、Et₃MeNBF₄、Et₃MeNClO₄、 Et₃MeNPF₆、Et₃MeNAsF₆、Et₃MeNSbF₆、Et₃MeNCF₃SO₃、Et₃MeN(CF₃SO₂)₂N、Et₃MeNC₄F₉SO₃；Particularly, Et can be enumerated₄NBF₄、Et₄NPF₆、Et₄NSbF₆、Et₄NAsF₆、Et₃MeNBF₄, N, N- diethyl-N- methyl-N- (2- methoxyl group Ethyl) ammonium salt etc..

(IIb) double pyrrolidines (spiro ring bipyrrolidinium) salt of loop coil

Preferably enumerate the double pyrrolidiniums of loop coil indicated by general formula (IIb-1), (IIb-2) or (IIb-3):

[changing 90]

(in formula, R^8aAnd R^9aIt is identical or different, it is the alkyl that carbon atom number is 1~4；X^-For anion；N1 is 0~5 Integer；The integer that n2 is 0~5.)

[changing 91]

(in formula, R^10aAnd R^11aIt is identical or different, it is the alkyl that carbon atom number is 1~4；X^-For anion；N3 is 0~5 Integer；The integer that n4 is 0~5.)

[changing 92]

(in formula, R^12aAnd R^13aIt is identical or different, it is the alkyl that carbon atom number is 1~4；X^-For anion；N5 is 0~5 Integer；The integer that n6 is 0~5.)

In addition, part or all of the hydrogen atom of the double pyrrolidiniums of the loop coil is 1~4 by fluorine atom and/or carbon atom number The compound that replaces of fluoro-alkyl, be also preferred from the viewpoint of oxidative resistance raising.

Anion X^-Preferred specific example with (IIa) the case where it is identical.Wherein, from dissociative under high, high voltage From the perspective of internal resistance is low, preferably BF₄-、PF₆-、(CF₃SO₂)₂N- or (C₂F₅SO₂)₂N-。

As the preferred specific example of the double pyrrolidiniums of loop coil, such as can enumerate

[changing 93]

Deng.

The double pyrrolidiniums of the loop coil are excellent in terms of the dissolubility, oxidative resistance, ionic conductivity that are dissolved in solvent.

(IIc) imidazole salts

Preferably enumerate the imidazole salts indicated by following general formula (IIc):

[changing 94]

(in formula, R^14aAnd R^15aIt is identical or different, it is the alkyl that carbon atom number is 1~6；X^-For anion.)

In addition, the fluoroalkane that part or all in the hydrogen atom of the imidazole salts is 1~4 by fluorine atom and/or carbon atom number The compound that base replaces is also preferred from the viewpoint of oxidative resistance raising.

Anion X^-Preferred specific example it is identical as (IIa).

As preferred specific example, such as following compound can be enumerated:

[changing 95]

Deng.

The imidazole salts are excellent in terms of sticky low and favorable solubility.

(IId): N- Fixanol

Preferably, the N- Fixanol indicated by following general formula (IId) can be enumerated:

[changing 96]

(in formula, R^16aThe alkyl for being 1~6 for carbon atom number；X^-For anion)

In addition, part or all of the hydrogen atom in the N- Fixanol is 1~4 by fluorine atom and/or carbon atom number The compound that fluoro-alkyl replaces is also preferred from the viewpoint of oxidative resistance raising.

Preferred anion X^-Specific example it is identical with (IIa).

As preferred specific example, such as following compound can be enumerated:

[changing 97]

Deng.

The N- Fixanol is excellent in terms of sticky low and favorable solubility.

(IIe) N, N- dialkyl pyrrolidinium salt

The N indicated by following general formula (IIe) is preferably enumerated, N- dialkyl pyrrolidinium salt:

[changing 98]

(in formula, R^17aAnd R^18aIt is identical or different, it is the alkyl that carbon atom number is 1~6；X^-For anion.)

In addition, part or all of the hydrogen atom of the N, N- dialkyl pyrrolidinium salt is 1 by fluorine atom and/or carbon atom number The compound that~4 fluoro-alkyl replaces is also preferred from the viewpoint of oxidative resistance raising.

Anion X^-Preferred specific example it is identical with (IIa).

As preferred specific example, such as following compound can be enumerated:

[changing 99]

[changing 100]

Deng.

The N, N- dialkyl pyrrolidinium salt are excellent in terms of sticky low and favorable solubility.

Among these ammonium salts, (IIa), (IIb) and (IIc) is good in dissolubility, oxidative resistance, ionic conductivity Aspect is preferred；Further preferred following compound.

[changing 101]

(in formula, Me is methyl；Et is ethyl；X^-, x, y it is identical with formula (IIa-1).)

In addition, lithium salts can be used as electric double layer capacitor solution matter salt.As lithium salts, such as preferred LiPF₆、 LiBF₄、LiAsF₆、LiSbF₆、LiN(SO₂C₂H₅)₂。

In order to further increase capacity, magnesium salts can be used.As magnesium salts, such as preferred Mg (ClO₄)₂、Mg(OOC₂H₅)₂Deng.

When electrolytic salt is above-mentioned ammonium salt, concentration is preferably 1.1 mol/Ls or more.If less than 1.1 mol/Ls, not only Low-temperature characteristics deteriorates, and initial internal resistance can also be got higher.The concentration of above-mentioned electrolytic salt is more preferably 1.25 mol/Ls or more.

In terms of low-temperature characteristics, above-mentioned concentration is preferably 1.7 mol/Ls hereinafter, below more preferably 1.5 mol/Ls.

When above-mentioned ammonium salt is triethylmethylammonium tetrafluoroborate (TEMABF₄) when, from the viewpoint of low-temperature characteristics is excellent, Concentration is preferably 1.1~1.4 mol/Ls.

In addition, when above-mentioned ammonium salt is the double pyrrolidines tetrafluoroborate (SBPBF of loop coil₄) when, preferably 1.3~1.7 moles/ It rises.

Electrolyte of the invention further preferably contain weight average molecular weight be 2000~4000, end have-OH ,-OCOOH, Or the polyoxyethylene of-COOH.

By containing such compound, the stability of electrode interface can be improved, improve the characteristic of electrochemical appliance.

As above-mentioned polyoxyethylene, such as polyoxyethylene monol, polyoxyethylene carboxylic acid, polyoxyethylene glycol, polyoxy second can be enumerated Docosene dicarboxylic acid, polyoxyethylene triol, polyoxyethylene tricarboxylic acids etc..They can be used alone, and can also be used in combination of two or more.

Wherein, from the viewpoint of the characteristic of electrochemical appliance becomes more good, preferably polyoxyethylene monol and polyoxy second The mixture of enediol and the mixture of polyoxyethylene carboxylic acid and polyoxyethylene dicarboxylic acids.

If above-mentioned polyoxyethylated weight average molecular weight is too small, easy to oxidize may decompose.Above-mentioned weight average molecular weight is more It is preferred that 3000~4000.

Above-mentioned weight average molecular weight can be by being measured based on the conversion of the polystyrene of gel permeation chromatography (GPC) method.

Above-mentioned polyoxyethylated content is preferably 1 × 10 in the electrolytic solution^-6~1 × 10^-2mol/kg.If above-mentioned polyoxy second The content of alkene is excessive, then may damage the characteristic of electrochemical appliance.

Above-mentioned polyoxyethylated content is more preferably 5 × 10^-6Mol/kg or more.

Electrolyte of the invention is also containing selected from being made of unsaturated cyclic carbonic ester and cyclic annular sulfoacid compound It is at least one kind of as additive in group.By containing these compounds, the reduction of battery behavior can be inhibited.

Above-mentioned unsaturated cyclic carbonic ester is the cyclic carbonate containing unsaturated bond, that is, has at least one in the molecule The cyclic carbonate of carbon-to-carbon unsaturated bond.Specifically, it such as can enumerate: vinylene carbonate, methylvinylene carbonate, second The esterification of the vinylene carbonates such as base vinylene carbonate, 4,5- dimethyl vinylene carbonate, 4,5- carbovinate vinylene Close object；4- vinylethylene carbonate (VEC), 4- methyl -4- vinylethylene carbonate, 4- ethyl -4- vinyl carbonic acid are sub- Ethyl ester, 4- n-propyl -4- vinylethylene carbonate, 5- methyl -4- vinylethylene carbonate, 4,4- divinyl carbonic acid are sub- Ethyl ester, 4,5- divinyl ethylene carbonate, 4,4- dimethyl -5- methene ethylene carbonate, 4,4- diethyl -5- methene Vinylethylene carbonates compound such as ethylene carbonate etc..Wherein, preferably vinylene carbonate, 4- vinyl carbonic acid Asia second Ester, 4- methyl -4- vinylethylene carbonate or 4,5- divinyl ethylene carbonate, particularly preferably vinylene carbonate, Or 4- vinylethylene carbonate.

The molecular weight of unsaturated cyclic carbonic ester is not particularly limited, as long as unobvious damage effect of the invention can be Arbitrary value.Molecular weight is preferably 50 or more, 250 or less.If in the range, it is easy to ensure that unsaturated cyclic carbonic ester dissolves In electrolyte dissolubility, be easy to fully demonstrate effect of the invention.The molecular weight of unsaturated cyclic carbonic ester is more preferably 80 More than, and more preferably 150 or less.

In addition, fluoro unsaturated cyclic carbonic ester also can be suitably used as unsaturated cyclic carbonic ester.

Number of fluorine atoms possessed by fluoro unsaturated cyclic carbonic ester is not particularly limited as long as being 1 or more.Wherein, fluorine atom Usually 6 hereinafter, preferably 4 hereinafter, most preferably fluorine atom is 1 or 2 fluoro unsaturated cyclic carbonic ester.

As fluoro unsaturated cyclic carbonic ester, fluoro vinylene carbonate ester derivant can be enumerated, by with aromatic rings or The fluoroethylene carbonate derivative etc. that the substituent group of carbon-to-carbon double bond replaces.

As fluoro vinylene carbonate ester derivant, 4- fluoro vinylene carbonate, 4- fluoro- 5- methyl carbonic acid Asia ethylene can be enumerated The fluoro- 5- phenyl-carbonic acid vinylene of ester, 4-, 4- allyl -5- fluoro vinylene carbonate, the fluoro- 5- vinyl carbonic acid Asia second of 4- Enester etc..

As the fluoroethylene carbonate derivative replaced by the substituent group with aromatic rings or carbon-to-carbon double bond, can enumerate: The fluoro- 4- vinylethylene carbonate of 4-, the fluoro- 4- allyl ethylene carbonate of 4-, the fluoro- 5- vinylethylene carbonate of 4-, 4- are fluoro- 5- allyl ethylene carbonate, the fluoro- 4- vinylethylene carbonate of 4,4- bis-, the fluoro- 4- allyl ethylene carbonate of 4,4- bis-, 4, The fluoro- 4,5- divinyl carbonic acid of the fluoro- 4- vinylethylene carbonate of 5- bis-, the fluoro- 4- allyl ethylene carbonate of 4,5- bis-, 4- is sub- Fluoro- 4, the 5- dietilenglycol ethyl of ethyl ester, 4-, fluoro- 4, the 5- divinyl ethylene carbonate of 4,5- bis-, 4,5- bis- fluoro- 4, The fluoro- 4- phenyl-carbonic acid ethyl of 5- dietilenglycol ethyl, 4-, the fluoro- 5- phenyl-carbonic acid ethyl of 4-, the fluoro- 5- of 4,4- bis- Phenyl-carbonic acid ethyl, the fluoro- 4- phenyl-carbonic acid ethyl of 4,5- bis- etc..

The molecular weight of fluoro unsaturated cyclic carbonic ester is not particularly limited, as long as unobvious damage effect of the invention It can be arbitrary value.Molecular weight is preferably 50 or more and is 500 or less.If in the range, it is easy to ensure that fluoric cyclic carbonic acid Ester is dissolved in the dissolubility of electrolyte, effect of the invention easy to accomplish.

Above-mentioned unsaturated cyclic carbonic ester can be used alone a kind, also can in any combination and ratio and with 2 kinds with On.

As above-mentioned cyclic annular sulfoacid compound, such as can to enumerate 1,3-propane sultone, Isosorbide-5-Nitrae-butane sultone, 1- fluoro- The fluoro- 1,3- propane sultone of 1,3- propane sultone, 2-, the fluoro- 1,3- propane sultone of 3- etc..Wherein, special from high temperature can be improved From the perspective of property, electrolyte of the invention preferably comprises 1,3-propane sultone, and/or Isosorbide-5-Nitrae-butane sultone.

When using at least 1 in the group being made of above-mentioned unsaturated cyclic carbonic ester and cyclic annular sulfoacid compound When kind compound is as additive, its content is preferably 0.1~10 mass % in electrolyte, more preferably 1 mass % or more, more Preferably 5 mass % or less.

Within the scope of the effect of the invention, electrolyte of the invention can be further containing cyclic annular and chain carboxylic Acid esters, ether compound, nitrogenous compound, boron-containing compound, organic silicon-containing compound, non-ignitable (fire-retardant) agent, surfactant, High dielectric constant additive, cycle characteristics and other solvents such as multiplying power property improver or overcharge preventing agent add Add agent.

As above-mentioned cyclic carboxylic esters, the total number of carbon atoms in its structural formula can be enumerated as 3~12 cyclic carboxylic esters.Tool Body, gamma-butyrolacton, gamma-valerolactone, γ-hexalactone, 6-caprolactone etc. can be enumerated.Wherein, from mentioning by lithium ion degree of dissociation From the perspective of the raising of high bring electrochemical appliance characteristic, particularly preferred gamma-butyrolacton.

The use level of cyclic carboxylic esters is preferably 0.1 mass % or more generally in the solvent of 100 mass %, more preferably 1 mass % or more.If in the range, being easy the conductivity for improving electrolyte, the heavy-current discharge for improving electrochemical appliance Characteristic.In addition, the use level of cyclic carboxylic esters is preferably 10 mass % hereinafter, more preferably 5 mass % or less.By setting this The upper limit of sample, the reduction for being easy to make the viscosity of electrolyte to be in suitable range, avoid conductivity, the increasing for inhibiting cathode resistance Greatly, it is easy to make the heavy-current discharge characteristic of electrochemical appliance to be in good range.

In addition, fluoric cyclic carboxylate (Fluorine-containing lactones) also can be suitably used as above-mentioned cyclic carboxylic esters.As fluorine-containing Lactone, such as the Fluorine-containing lactones indicated by following formula (E) can be enumerated:

[changing 102]

(in formula, X¹⁵~X²⁰It is identical or different, it is-H ,-F ,-Cl ,-CH₃Or fluoro-alkyl；Wherein, X¹⁵~X²⁰In At least one is fluoro-alkyl.)

As X¹⁵~X²⁰In fluoro-alkyl, such as-CFH can be enumerated₂、-CF₂H、-CF₃、-CH₂CF₃、-CF₂CF₃、- CH₂CF₂CF₃、-CF(CF₃)₂Deng, from the viewpoint of oxidative resistance height, having the effect of improving safety, preferably-CH₂CF₃、- CH₂CF₂CF₃。

If X¹⁵~X²⁰In at least one be fluoro-alkyl, then-H ,-F ,-Cl ,-CH₃Or fluoro-alkyl can be to X¹⁵~X²⁰In Only replaced at 1, many places can also be replaced.From the viewpoint of the favorable solubility of electrolytic salt, preferably 1~3 Locate, at more preferably 1~2.

The position of substitution of fluoro-alkyl is not particularly limited, but from the good viewpoint of synthesis yield, preferably X¹⁷With/ Or X¹⁸, particularly X¹⁷Or X¹⁸For fluoro-alkyl, wherein fluoro-alkyl is preferably-CH₂CF₃、-CH₂CF₂CF₃.Except fluoro-alkyl with Outer X¹⁵~X²⁰For-H ,-F ,-Cl or CH₃, particularly, from the viewpoint of the favorable solubility of electrolytic salt, preferably-H.

As Fluorine-containing lactones, other than the Fluorine-containing lactones indicated by above-mentioned formula, also it can be mentioned, for example by following formula (F) table The Fluorine-containing lactones etc. shown:

[changing 103]

(in formula, any one in A and B is CX²⁶X²⁷(X²⁶And X²⁷It is identical or different, be-H ,-F ,-Cl ,- CF₃、-CH₃Or hydrogen atom can be replaced by halogen atom, heteroatomic alkylidene can be contained in chain), another one is oxygen atom； Rf¹²For that can have the fluoro-alkyl or fluoroalkyl of ehter bond；X²¹And X²²It is identical or different, it is-H ,-F ,-Cl ,-CF₃、 Or CH₃；X²³~X²⁵It is identical or different, be it is that-H ,-F ,-Cl or hydrogen atom can be replaced by halogen atom, miscellaneous original can be contained in chain The alkyl of son；N=0 or 1.)

As the Fluorine-containing lactones indicated by formula (F), the viewpoint from the viewpoint being readily synthesized, chemically having good stability goes out Hair preferably enumerates 5 ring structures indicated by following formula (G):

[changing 104]

(in formula, A, B, Rf¹²、X²¹、X²²And X²³It is identical with formula (F).)

Further, according to the combination of A and B, including the Fluorine-containing lactones by following formula (H) and the expression of following formula (I)s:

[changing 105]

(in formula, Rf¹²、X²¹、X²²、X²³、X²⁶And X²⁷It is identical with formula (F).)

[changing 106]

Among them, from terms of it can especially play the excellent characteristics such as high dielectric constant, high proof voltage and electrolyte From the perspective of the favorable solubility of salt, the good aspect of reduction of internal resistance improve the characteristic of electrolyte of the invention, it can enumerate Following Fluorine-containing lactones:

[changing 107]

Deng.

By making electrolyte contain fluoric cyclic carboxylate, when can obtain improving ionic conductivity, improving safety, improve high temperature Stability and other effects.

As above-mentioned chain carboxylate, the total number of carbon atoms in its structural formula can be enumerated as 3~7 chain carboxylate.Tool Body, it can enumerate: methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second Tert-butyl acrylate, methyl propionate, ethyl propionate, n propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, propionic acid uncle Butyl ester, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, methyl isobutyrate, ethyl isobutyrate, isobutyric acid positive third Ester, isopropyl isobutyrate etc..

Wherein, from the viewpoint of viscosity reduce thus ionic conductivity improves, preferably methyl acetate, ethyl acetate, second Sour n-propyl, n-butyl acetate, methyl propionate, ethyl propionate, n propyl propionate, isopropyl propionate, methyl butyrate and butyric acid Ethyl ester etc..

In addition, fluoro chain carboxylate also can be suitably used.As fluorinated ester, it is high from anti-flammability and with other solvents From the perspective of intermiscibility is good, oxidative resistance is good, preferably by the fluoro chain carboxylate of following formula (J) expression:

Rf¹⁰COORf¹¹ (J)

(in formula, Rf¹⁰The fluoro-alkyl for being 1~2 for carbon atom number, Rf¹¹The fluoro-alkyl for being 1~4 for carbon atom number.)

As Rf¹⁰, such as CF can be enumerated₃-、CF₃CF₂-、HCF₂CF₂-、HCF₂-、CH₃CF₂And CF₃CH₂Etc., In, from the viewpoint of multiplying power property is good, particularly preferred CF₃And CF₃CF₂-。

As Rf¹¹, such as CF can be enumerated₃-、CF₃CF₂-、(CF₃)₂CH-、CF₃CH₂-、CF₃CH₂CH₂-、 CF₃CFHCF₂CH₂-、C₂F₅CH₂-、CF₂HCF₂CH₂-、C₂F₅CH₂CH₂-、CF₃CF₂CH₂And CF₃CF₂CF₂CH₂Etc., wherein From the viewpoint of with the intermiscibility of other solvents it is good, particularly preferred CF₃CH₂-、(CF₃)₂CH-、C₂F₅CH₂And CF₂HCF₂CH₂-。

As the specific example of fluoro chain carboxylate, such as CF can be enumerated₃C (=O) OCH₂CF₃、CF₃C (=O) OCH₂CH₂CF₃、CF₃C (=O) OCH₂C₂F₅、CF₃C (=O) OCH₂CF₂CF₂H、CF₃C (=O) OCH (CF₃)₂1 kind in or 2 kinds More than, wherein from the viewpoint of with the intermiscibility and multiplying power property of other solvents it is good, particularly preferred CF₃C (=O) OCH₂C₂F₅、CF₃C (=O) OCH₂CF₂CF₂H、CF₃C (=O) OCH₂CF₃And CF₃C (=O) OCH (CF₃)₂。

As above-mentioned ether compound, preferably carbon atom number be 3~10 chain ether and carbon atom number be 3~6 ring-type Ether.

The chain ether for being 3~10 as carbon atom number, can enumerate: diethyl ether, di-n-butyl ether, dimethoxymethane, methoxyl group second Oxygroup methane, diethoxymethane, dimethoxymethane, methoxyethoxyethane, diethoxyethane, ethylene glycol two positive third Ether, ethylene glycol di-n-butyl ether, diethylene glycol dimethyl ether etc..

In addition, fluoro-ether also can be suitably used as above-mentioned ether compound.

As above-mentioned fluoro-ether, the fluoro-ether (K) indicated by the following general formula (K) can be enumerated:

Rf¹-O-Rf² (K)

(in formula, Rf¹And Rf²It is identical or different, it is the alkyl that carbon atom number is 1~10 or the fluoro that carbon atom number is 1~10 Alkyl.Wherein, Rf¹And Rf²In at least 1 be fluoro-alkyl.)

By contain fluoro-ether (K), can improve electrolyte anti-flammability while, improve high temperature high voltage under stability, Safety.

In above-mentioned general formula (K), Rf¹And Rf²At least one in as long as be carbon atom number be 1~10 fluoro-alkyl i.e. Can, still, from the viewpoint of under the anti-flammability and high temperature high voltage for further increasing electrolyte stability, safety, It is preferred that Rf¹And Rf²It is simultaneously the fluoro-alkyl that carbon atom number is 1~10.At this point, Rf¹And Rf²Can be identical, it can also be each other It is different.

Wherein, it is further preferred that Rf¹And Rf²It is identical or different, Rf¹For carbon atom number be 3~6 fluoro-alkyl and Rf²For The fluoro-alkyl that carbon atom number is 2~6.

If Rf¹And Rf²Total carbon atom number it is very few, then the boiling point of fluoro-ether becomes too low；In addition, if Rf¹Or Rf²'s Carbon atom number is excessive, then the dissolubility of electrolytic salt reduces, also starts to adversely affect to the intermiscibility with other solvents, and And multiplying power property is caused to reduce since viscosity rises.Work as Rf¹Carbon atom number be 3 or 4, Rf²Carbon atom number be 2 or 3 when, It is advantageous in terms of boiling point and excellent multiplying power property.

The fluorine content of above-mentioned fluoro-ether (K) is preferably 40~75 mass %.When the fluorine content with the range, noninflammability It is balanced with intermiscibility especially excellent.In addition, from the viewpoint of oxidative resistance, good security, and it is preferred.

The lower limit of above-mentioned fluorine content is more preferably 45 mass %, further preferably 50 mass %, particularly preferably 55 mass %. The upper limit is more preferably 70 mass %, further preferably 66 mass %.

In addition, the fluorine content of fluoro-ether (K) is the structural formula for being based on fluoro-ether (K), according to { (number × 19 of fluorine atom)/fluorine For the molecular weight of ether (K) } × 100 (%) calculate value.

As Rf¹, such as can enumerate: CF₃CF₂CH₂-、CF₃CFHCF₂-、HCF₂CF₂CF₂-、HCF₂CF₂CH₂-、 CF₃CF₂CH₂CH₂-、CF₃CFHCF₂CH₂-、HCF₂CF₂CF₂CF₂-、HCF₂CF₂CF₂CH₂-、HCF₂CF₂CH₂CH₂And HCF₂CF (CF₃)CH₂Etc..

In addition, as Rf², such as can enumerate: CF₃CF₂CH₂-、CF₃CFHCF₂-、CF₂HCF₂CF₂-、CF₂HCF₂CH₂-、 CF₃CF₂CH₂CH₂-、CF₃CFHCF₂CH₂-、CF₂HCF₂CF₂CF₂-、CF₂HCF₂CF₂CH₂-、CF₂HCF₂CH₂CH₂-、CF₂HCF(CF₃) CH₂-、CF₂HCF₂-、CF₂HCH₂And CH₃CF₂Etc..

It as the specific example of above-mentioned fluoro-ether (K), such as can enumerate: HCF₂CF₂CH₂OCF₂CF₂H、 CF₃CF₂CH₂OCF₂CF₂H、HCF₂CF₂CH₂OCF₂CFHCF₃、CF₃CF₂CH₂OCF₂CFHCF₃、C₆F₁₃OCH₃、C₆F₁₃OC₂H₅、 C₈F₁₇OCH₃、C₈F₁₇OC₂H₅、CF₃CFHCF₂CH(CH₃)OCF₂CFHCF₃、HCF₂CF₂OCH(C₂H₅)₂、HCF₂CF₂OC₄H₉、 HCF₂CF₂OCH₂CH(C₂H₅)₂And HCF₂CF₂OCH₂CH(CH₃)₂Deng.

Wherein, contain HCF in an end or two ends₂Or CF₃It can obtain that polarizability is excellent, boiling point is high when CFH- Fluoro-ether (K).The boiling point of fluoro-ether (K) is preferably 67~120 DEG C.More preferably 80 DEG C or more, further preferably 90 DEG C with On.

As such fluoro-ether (K), such as CF can be enumerated₃CH₂OCF₂CFHCF₃、CF₃CF₂CH₂OCF₂CFHCF₃、 HCF₂CF₂CH₂OCF₂CFHCF₃、HCF₂CF₂CH₂OCH₂CF₂CF₂H、CF₃CFHCF₂CH₂OCF₂CFHCF₃、 HCF₂CF₂CH₂OCF₂CF₂And CF H,₃CF₂CH₂OCF₂CF₂It is one kind or two or more in H etc..

Wherein, from higher boiling, with the intermiscibilities of other solvents is good, advantageous sight in terms of favorable solubility of electrolytic salt Point sets out, and is preferably selected from by HCF₂CF₂CH₂OCF₂CFHCF₃(106 DEG C of boiling point), CF₃CF₂CH₂OCF₂CFHCF₃(boiling point 82 ℃)、HCF₂CF₂CH₂OCF₂CF₂H (92 DEG C of boiling point) and CF₃CF₂CH₂OCF₂CF₂In the group of H (68 DEG C of boiling point) composition at least One kind, more preferably selected from by HCF₂CF₂CH₂OCF₂CFHCF₃(106 DEG C of boiling point) and HCF₂CF₂CH₂OCF₂CF₂H (boiling point 92 DEG C) at least one of the group of composition.

The cyclic ether for being 3~6 as carbon atom number, can enumerate 1,3- dioxanes, 2- methyl-1,3- dioxanes, 4- methyl- 1,3- dioxanes, Isosorbide-5-Nitrae-dioxanes etc. and their fluoric compound.Wherein, high from the solvability to lithium ion, mention From the perspective of macroion degree of dissociation, preferably dimethoxymethane, diethoxymethane, ethoxymethyl) epoxide methane, ethylene glycol Positive propyl ether, ethylene glycol di-n-butyl ether and diethylene glycol dimethyl ether.From the viewpoint low, that high ionic conductivity can be provided of viscosity It sets out, particularly preferred dimethoxymethane, diethoxymethane and ethoxymethyl) epoxide methane.

As above-mentioned nitrogenous compound, can enumerate nitrile, fluorinated nitrile, carboxylic acid amide, fluorine-containing carboxylic acid amide, sulfonic acid amides and Sulfonic fluoropolymer amide etc..In addition, it is possible to use 1-Methyl-2-Pyrrolidone, 1- methyl -2- piperidones, 3- methyl -2- oxazolidine Ketone (3-methyl-2-oxazolidinone), 1,3- dimethyl-2-imidazolinone (1,3-dimethyl-2- ) and N methyl succinimide etc. imidazolidinone.

As above-mentioned boron-containing compound, for example, can enumerate the borates such as trimethylborate, triethyl borate, boric acid ether, with And alkyl borane etc..

As above-mentioned organic silicon-containing compound, such as (CH can be enumerated₃)₄-Si、(CH₃)₃-Si-Si(CH₃)₃Deng.

As above-mentioned non-ignitable (fire-retardant) agent, phosphate, phosphorus nitrile compounds can be enumerated.As above-mentioned phosphate, such as It can enumerate containing fluoroalkyl phosphates, non-fluorine system alkyl phosphate, aryl phosphate ester etc..Wherein, from can be can play not on a small quantity From the aspect of fuel efficiency fruit, preferably contain fluoroalkyl phosphates.

It can specifically be enumerated disclosed in Japanese Unexamined Patent Publication 11-233141 bulletin as above-mentioned containing fluoroalkyl phosphates Cyclic alkyl phosphate disclosed in fluorine-containing dialkyl phosphate, Japanese Unexamined Patent Publication 11-283669 bulletin or fluorine-containing three alkane Base phosphate etc..

As above-mentioned non-ignitable (fire-retardant) agent, preferably (CH₃O)₃P=O, (CF₃CH₂O)₃P=O, (HCF₂CH₂O)₃P=O, (CF₃CF₂CH₂)₃P=O and (HCF₂CF₂CH₂)₃P=O etc..

As above-mentioned surfactant, cationic surfactant, anionic surfactant, non-ionic surface Any one in activating agent and amphoteric surfactant, but, multiplying power property good viewpoint good from cycle characteristics It sets out, preferably containing the surfactant of fluorine atom.

As such surfactant containing fluorine atom, such as preferably

By following formula:

Rf¹COO^-M⁺

Indicate fluorine-containing carboxylate (in formula, Rf¹For carbon atom number be 3~10, fluoro-alkyl containing ehter bond；M⁺For Li⁺、 Na⁺、K⁺Or NHR '₃ ⁺(R ' is identical or different, is the alkyl that H or carbon atom number are 1~3)),

By following formula:

Rf²SO₃ ^-M⁺

Expression sulfonic fluoropolymer salt (in formula, Rf²For carbon atom number be 3~10, fluoro-alkyl containing ehter bond；M⁺For Li⁺、 Na⁺、K⁺Or NHR '₃ ⁺(R ' is identical or different, is the alkyl that H or carbon atom number are 1~3)) etc..

From the viewpoint of can in the case where not reducing charge/discharge cycle characteristics reduce electrolyte surface tension, electrolysis The content of above-mentioned surfactant is preferably 0.01~2 mass % in liquid.

As above-mentioned high dielectric constant additive, such as sulfolane, methyl sulfolane, gamma-butyrolacton, γ-can be enumerated Valerolactone, acetonitrile, propionitrile etc..

As above-mentioned cycle characteristics and multiplying power property improver, such as methyl acetate, ethyl acetate, tetrahydro furan can be enumerated It mutters, 1,4- dioxanes etc..

As above-mentioned overcharge preventing agent, from can inhibit in overcharge etc. battery rupture it is on fire from the aspect of, Preferably with the overcharge preventing agent of aromatic rings.It as the above-mentioned overcharge preventing agent with aromatic rings, such as can enumerate: ring Hexyl benzene, biphenyl, alkyl biphenyl, terphenyl, terphenyl part hydride, tert-butyl benzene, tert-amyl benzene, diphenyl ether, benzo The aromatic compounds such as furans, dibenzofurans, dichloroaniline, toluene；Phenyl-hexafluoride, fluorobenzene, 2- fluorine biphenyl, adjacent cyclohexyl fluorine Benzene, the fluoro object to aromatic compounds such as cyclohexyl fluorobenzene；2,4 difluorobenzene methyl ether, 2,5- difluoroanisole, 2,6- difluoro Fluorine-containing benzyl ether compounds such as methyl phenyl ethers anisole, 3,5- difluoroanisole etc..Wherein, preferably biphenyl, alkyl biphenyl, terphenyl, three The aromatic compounds such as part hydride, cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene, diphenyl ether and the dibenzofurans of benzene Object.They can be used alone a kind, can also be used in combination of two or more.When being used in combination of two or more, particularly, from overcharge prevention characteristics From the aspect of balanced between High temperature storage characteristic, preferably the combination of cyclohexyl benzene and tert-butyl benzene or tert-amyl benzene, with And no selected from biphenyl, alkyl biphenyl, terphenyl, the part hydride of terphenyl, cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene etc. In oxygen containing aromatic compound it is at least one kind of in the oxygen-containing aromatic compound such as diphenyl ether, dibenzofurans extremely Few a kind of combination.

From can be prevented when overcharge battery rupture, it is on fire from the aspect of, above-mentioned overcharge prevents in electrolyte The content of agent is preferably 0.1~5 mass %.

In the range of not destroying effect of the invention, electrolyte of the invention can also contain other well known auxiliary agents.Make It for above-mentioned auxiliary agent well known to other, such as can enumerate: anhydroerythritol carbonic ester (erythritan carbonate), loop coil- The carbonate products such as double-dimethylene carbonic ester, methoxy ethyl-methyl carbonic；Tetra- oxaspiro of 2,4,8,10- [5.5] The spiro-compounds such as hendecane, 3,9- divinyl -2,4,8,10- four oxaspiro [5.5] hendecane；Glycol sulfite, fluorine Methylmesylate, ethyl fluorosulfonate, methyl methylsulfonate, ethylmethane sulfonate, busulfan, cyclobufene sultone, diphenyl sulphone (DPS), N, N- diformazan Base Methanesulfomide, N, the chain sulfones such as N- diethyl Methanesulfomide, fluorine-containing chain sulfone, chain sulphonic acid ester, fluorine-containing chain sulphonic acid ester, ring The sulfur-containing compounds such as shape sulfone, fluorine-containing cyclic sulfones, sulfonic acid halide and fluorine-containing sulfonic acid halide；Heptane, octane, nonane, decane, cycloheptane etc. Hydrocarbon compound etc..They can be used alone a kind, can also be used in combination of two or more.By adding these auxiliary agents, high temperature dwell can be improved Capacity maintenance characteristics, cycle characteristics after depositing.

In addition, electrolyte of the invention can also combine the gel electrolyte that gel (after plasticising) is made with high molecular material Liquid.

As such high molecular material, can enumerate: known polyoxyethylene, polyoxypropylene and they change Property body (Japanese Unexamined Patent Publication 8-222270 bulletin, Japanese Unexamined Patent Publication 2002-100405 bulletin)；Polyacrylate based polymer, The fluorine such as polyacrylonitrile, polyvinylidene fluoride (Polyvinylidene fluoride), vinylidene difluoride-hexafluoropropylene copolymer Resin (Japanese Kohyo 4-506726 bulletin, Japanese Kohyo 8-507407 bulletin, Japanese Unexamined Patent Publication 10-294131 Bulletin)；Compound (the Japanese Unexamined Patent Publication 11-35765 bulletin, Japanese Unexamined Patent Publication 11- of these fluororesin and hydrocarbon resins No. 86630 bulletins) etc..In particular it is preferred to which polyvinylidene fluoride, vinylidene difluoride-hexafluoropropylene copolymer are used as gel electricity Xie Zhiyong high molecular material.

In addition, electrolyte of the invention is led containing the ion recorded in Japanese Patent Application 2004-301934 specification Conductive compounds.

The ionic conductivity compound is by formula (1-1):

A-(D)-B (1-1)

What is indicated has the amorphism Fluoropolyether compound of fluoro-containing group in side chain.

[in formula (1-1),

D is by formula (2-1):

-(D1)_n-(FAE)_m-(AE)_p-(Y)_q- (2-1)

It indicates.

A and B are identical or different, are hydrogen atom, the alkyl containing fluorine atom and/or cross-linking functional group, can contain fluorine original (R is hydrogen atom or can contain fluorine atom and/or bridging property function by son and/or the phenyl of cross-linking functional group ,-COOH base ,-OR The alkyl of group), ester group or carbonate group (wherein, when the end of D is oxygen atom A, B be not -COOH base ,-OR, ester group, with And carbonate group).

(in formula (2-1),

D1 is to be indicated by following formula (2a) in ether unit of the side chain with fluorine-containing ether:

[changing 108]

(in formula (2a), Rf is the fluorine-containing ether that can have cross-linking functional group；R¹⁰For bonding Rf and main chain group or Key.)；

FAE is to be indicated by following formula (2b) in ether unit of the side chain with fluoro-alkyl:

[changing 109]

(in formula (2b), Rfa is hydrogen atom or the fluoro-alkyl that can have cross-linking functional group；R¹¹For bonding Rfa and master The group or key of chain.)；

AE is the ether unit indicated by formula (2c):

[changing 110]

(in formula (2c), R¹³For hydrogen atom, the alkyl that can have cross-linking functional group, the rouge that can have cross-linking functional group Fat race ring type alkyl or the aromatic hydrocarbyl that can have cross-linking functional group；R¹²To be bonded R¹³With the group or key of main chain.)；

Y is the unit containing at least one kind of structure in following formula (2d-1)~(2d-3):

[changing 111]

In formula (2-1), n be 0~200 integer；The integer that m is 0~200；The integer that p is 0~10000；Q is 1~100 Integer；Wherein, n+m is not 0, and the bonding sequence of D1, FAE, AE and Y are not specified.)]

As needed, other additives can also be cooperated in electrolyte of the invention.As other additives, such as can enumerate Metal oxide, glass etc..

Electrolyte of the invention preferably comprises the HF of 0.5~200ppm.By containing HF, it can promote additive formation and cover Film.If the content of HF is very few, additive forms the ability decline of overlay film on cathode, and battery behavior has reduced tendency. In addition, due to the influence of HF, the oxidative resistance of electrolyte has reduced tendency if HF content is excessive.Electrolysis of the invention Even if HF of the liquid containing above range, the high temperature dwell sustainability and capacity restoration rate of battery will not be reduced.

The content of HF is more preferably 1ppm or more, further preferably 2.5ppm or more.Also, the content of HF is more preferably 150ppm hereinafter, further preferably 100ppm hereinafter, particularly preferably 80ppm or less.

The content of HF can be measured by neutralization titration.

Said components can be used to prepare with any means for electrolyte of the invention.

Electrolyte of the invention can for example be suitably applied to the electrochemistry such as lithium ion secondary battery, double layer capacitor dress It sets.Such electrochemical appliance for having electrolyte of the invention is also one aspect of the present invention.

As electrochemical appliance, can enumerate: lithium ion secondary battery, capacitor (double layer capacitor), free base battery, Solar battery (especially dye-sensitized solar cell), fuel cell, various electrochemical sensors, electrochromism member Part, electrochemical switch element, aluminium electrolutic capacitor, tantalum electrolytic capacitor etc.；It is preferred that lithium ion secondary battery, electric double layer capacitance Device.

The component for having above-mentioned electrochemical appliance is also one aspect of the present invention.

The present invention also relates to the lithium ion secondary batteries for having electrolyte of the invention.Above-mentioned lithium ion secondary battery can have Standby anode, cathode and above-mentioned electrolyte.

< anode >

Anode is made of the positive electrode active material layer containing positive active material and collector.

As above-mentioned positive active material, without special as long as it can electrochemically make lithium ion be embedded in deintercalation Limitation, such as preferably comprise the substance of lithium and at least one kind of transition metal.As specific example, the transition metal containing lithium can be enumerated Composite oxides, the transition metal phosphate compound containing lithium.Wherein, as a positive electrode active material, in particular it is preferred to which output is high The compound transition metal oxide containing lithium of voltage.

As the above-mentioned compound transition metal oxide containing lithium, such as can enumerate:

By formula: Li_aMn_2-bM¹ _bO₄(in formula, 0.9≤a；0≤b≤1.5；M¹For selected from by Fe, Co, Ni, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si and Ge composition group at least one kind of metal) indicate lithium manganese spinel it is compound Oxide,

By formula: LiNi_1-cM² _cO₂(in formula, 0≤c≤0.5；M²For selected from by Fe, Co, Mn, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si and Ge composition group at least one kind of metal) indicate lithium nickel composite oxide, or

By formula: LiCo_1-dM³ _dO₂(in formula, 0≤d≤0.5；M³For selected from by Fe, Ni, Mn, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si and Ge composition group at least one kind of metal) indicate lithium cobalt composite oxide.

Wherein, from the viewpoint of the lithium ion secondary battery that can provide high, the high output of energy density, preferably LiCoO₂、 LiMnO₂、LiNiO₂、LiMn₂O₄、LiNi_0.8Co_0.15Al_0.05O₂Or LiNi_1/3Co_1/3Mn_1/3O₂。

As other above-mentioned positive active materials, LiFePO can be enumerated₄、LiNi_0.8Co_0.2O₂、Li_1.2Fe_0.4Mn_0.4O₂、 LiNi_0.5Mn_0.5O₂、LiV₃O₆、Li₂MnO₃Deng.

Particularly, if using Li₂MnO₃、LiNi_0.5Mn_0.5O₂Equal positive active materials, though then be more than 4.4V voltage, Lithium ion secondary battery is set to work under the voltage of 4.6V or more, the crystal structure of above-mentioned positive active material will not destroy.Into One step, electrolyte of the invention is not oxidizable loading high voltage due to above-mentioned composition.Therefore, from i.e. Make to store that residual capacity is also not easy to reduce, resistance increment rate is also not easy to change at high temperature, and even if works under high voltages The viewpoint that battery performance will not deteriorate is set out, and has electrolyte of the invention and by containing foregoing illustrative positive-active The electrochemical appliances such as the lithium ion secondary battery of anode that the positive electrode active material layer and collector of substance are constituted are preferred.

In addition, trickle charge characteristic is improved, is therefore preferred if positive active material is made to contain lithium phosphate.In phosphorus There is no limit in the use of sour lithium, but preferably mixes positive active material above-mentioned with lithium phosphate and use.Relative to above-mentioned The total amount of positive active material and lithium phosphate, the lower limit of the amount of the lithium phosphate used are preferably 0.1 mass % or more, more preferably 0.3 mass % or more, further preferably 0.5 mass % or more；The upper limit is preferably 10 mass % hereinafter, more preferably 8 matter % is measured hereinafter, further preferably 5 mass % or less.

In addition, the surface that can be used on above-mentioned positive active material is attached to the substance of different composition and obtains Structure.It as surface attachment, can enumerate: aluminium oxide, silica, titanium oxide, zirconium oxide, magnesia, calcium oxide, oxidation The oxides such as boron, antimony oxide, bismuth oxide, the sulfate such as lithium sulfate, sodium sulphate, potassium sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, carbon The carbonate such as sour lithium, calcium carbonate, magnesium carbonate, carbon etc..

These surface attachments, such as can be allowed to be attached to the positive active material surface by following methods: make table Face attachment material dissolves or is suspended in solvent, is dipped into being added to method on the positive active material and dry；Make surface Attachment material precursor dissolve or be suspended in solvent, be dipped into after being added on the positive active material, by heating etc. come It is allowed to the method reacted；The method etc. that surface attachment is added to positive active material precursor, while is burnt into.In addition, working as When adhering to carbon, the method that adheres to carbonaceous for example in subsequent mechanical in the form of active carbon etc..

As the amount of surface attachment, relative to above-mentioned positive active material, in mass in the case where, as under Limit more preferably uses 1ppm or more, further preferably uses 10ppm or more, it is preferable to use 0.1ppm or more；It is excellent as the upper limit Choosing is using 20% hereinafter, more preferably using 10% hereinafter, further preferably 5% or less.Using surface attachment, can inhibit The oxidation reaction of electrolyte at positive active material surface, can be improved battery life.It, can but when its adhesion amount is very few The effect can sufficiently be showed；When excessive, due to interfering the discrepancy of lithium ion, resistance may be will increase.

The shape of positive active material particle can enumerate bulk such as previous use, polyhedral, spherical, ellipse Spherical, plate, needle-shaped and column etc..In addition, primary particle can also be assembled to form offspring.

The tap density of positive active material is preferably 0.5g/cm³More than, more preferably 0.8g/cm³More than, it is further excellent It is selected as 1.0g/cm³More than.If the tap density of the positive active material is lower than above-mentioned lower limit, when formation positive active material When layer, with the increase of required decentralized medium amount, sometimes the requirement increase of conductive material, binder, positive active material It is restricted to the filling rate of positive electrode active material layer, battery capacity is restricted.By using the high composite oxygen of tap density Compound powder can form highdensity positive electrode active material layer.Tap density is generally the bigger the better, without the specific upper limit, but It is, if excessive, using the electrolyte in positive electrode active material layer as the limited speed of the diffusion of the lithium ion of medium, load characteristic It is sometimes prone to reduce, therefore, the upper limit is preferably 4.0g/cm³, more preferably 3.7g/cm³, further preferably 3.5g/cm³,.

In addition, in the present invention, tap density be as 5~10g of positive active material powder is put into 10ml glass system graduated cylinder, Powder filled density (tap density) g/cm when being shaken 200 times with the amplitude of about 20mm³It finds out.

The median diameter d50 of positive active material particle (is secondary grain when primary particles aggregate is formed as offspring Sub- diameter) it is preferably 0.3 μm or more, more preferably 0.5 μm or more, further preferably 0.8 μm or more, most preferably 1.0 μm More than；Also, preferably 30 μm hereinafter, more preferably 27 μm hereinafter, further preferably 25 μm hereinafter, most preferably 22 μm with Under.When being lower than above-mentioned lower limit, the product of high-tap density cannot be obtained sometimes；When being more than the upper limit, due to the lithium in particle Diffusion it is time-consuming, therefore sometimes result in battery performance reduction；Or make battery anode when, i.e., by active material with Conductive material, adhesive etc. with solvent carry out it is slurried and be coated be film-form when, sometimes generate there is the problems such as striped.This Place can further increase system by mixing the above-mentioned positive active material of more than two kinds with different median diameter d50 Make fillibility when anode.

In addition, in the present invention, median diameter d50 using well known laser diffraction/scattering formula particle size distribution device into Row measurement.When using HORIBA, Ltd. LA-920 uses the calgon water of 0.1 mass % as size distribution timing The decentralized medium used when solution is as measurement, the ultrasonic wave carried out 5 minutes will measure refractive index after dispersing and be set as 1.24 progress Measurement.

When primary particles aggregate forms offspring, as the average primary particle diameter of above-mentioned positive active material, preferably It is 0.05 μm or more, more preferably 0.1 μm or more, further preferably 0.2 μm or more；The upper limit is preferably 5 μm, more preferably 4 μ M, further preferably 3 μm, most preferably 2 μm.If being more than the above-mentioned upper limit, it is difficult to form spherical offspring, is filled out to powder Filling property brings adverse effect；Moreover, because a possibility that specific surface area substantially reduces, therefore the battery performances such as output characteristics reduce Sometimes it will increase.Conversely, if being lower than above-mentioned lower limit, it usually may be due to crystallizing invertibity that is undeveloped and generating charge and discharge The problems such as poor.

In addition, primary particle size is measured by using the observation of scanning electron microscope (SEM) in the present invention.Specifically Ground, can be by finding out the left bounding lines of primary particle to water to any 50 primary particles in the photo of 10000 times of multiplying powers Square to straight line intercept greatest length, be averaged to find out.

The BET specific surface area of positive active material is preferably 0.1m²/ g or more, more preferably 0.2m²/ g or more, further Preferably 0.3m²/ g or more；The upper limit is preferably 50m²/ g, more preferably 40m²/ g, further preferably 30m²/g.If BET compares table The area ratio range is small, then battery performance is easily reduced, if than the range greatly if tap density be not easy to improve, may be living in anode Property material layer formation when coating in terms of be easy to produce problem.

In addition, BET specific surface area is defined as the value measured by the following method in the present invention: using surface area meter (such as Ohkura Riken Co.Ltd., make full-automatic surface area determination unit), nitrogen circulation under with 150 DEG C to sample into After row predrying in 30 minutes, mixed using the nitrogen helium that the relative pressure of the nitrogen relative to atmospheric pressure is accurately adjusted to 0.3 Gas is measured using the N2 adsorption BET1 point method based on gas flow method.

When lithium ion secondary battery of the invention is used as Hybrid Vehicle, the large-scale lithium ion secondary of distributed generation resource When battery, due to needing high output, it is therefore preferable that in the particle of above-mentioned positive active material based on offspring.

Above-mentioned positive active material particle is preferably that the average particle diameter of offspring is 40 μm or less and contains 0.5~7.0 body The average primary particle diameter of product % is 1 μm of particle below.By being 1 μm of particle below containing average primary particle diameter, it is possible to increase With the contact area of electrolyte, make the diffusion of lithium ion between electrode and electrolyte faster.As a result, the defeated of battery can be improved Performance out.

The common side of the manufacturing method as inorganic compound can be used in manufacturing method as a positive electrode active material Method.Particularly, it may be considered that various methods make spherical or ellipsoid active material, such as the following method can be enumerated etc.: Raw material dissolution or grinding dispersion by transition metal adjust pH while stirring, make spherical precursor in water equal solvent And recycle, as needed by drying, thereafter be added LiOH, Li₂CO₃、LiNO₃The equal source Li, high temperature firing obtain active material.

In order to manufacture anode, positive active material above-mentioned can be used alone, can also by different compositions two or more with appoint The combination of meaning or ratio are used in combination.As preferred combination at this time, LiCoO can be enumerated₂With LiNi_0.33Co_0.33Mn_0.33O₂Deng LiMn₂O₄Or combination or and the LiCoO of a part of its Mn compound obtained from the substitution such as other transition metal₂Or The combination of compound obtained from a part of its Co is substituted by other transition metal etc..

From the aspect of battery capacity height, the content of above-mentioned positive active material is preferably 50~99 matter of anode mixture Measure %, more preferably 80~99 mass %.In addition, the content of positive active material is preferably 80 matter in positive electrode active material layer Measure % or more, more preferably 82 mass % or more, particularly preferably 84 mass % or more.Moreover, the upper limit is preferably 99 mass %, More preferably 98 mass %.If the content of the positive active material in positive electrode active material layer is low, capacitance may be inadequate. Conversely, the intensity of anode may be insufficient if too high levels.

It is preferred that above-mentioned anode mixture also contains binder, thickener and conductive material.

As above-mentioned binder, as long as the material of the solvent, electrolyte safety that use when manufacture electrode may be used and be appointed The binder of meaning, such as can enumerate: polyvinylidene fluoride, polytetrafluoroethylene (PTFE), polyethylene, polypropylene, SBR (styrene-butadiene Rubber), it is isoprene rubber, butadiene rubber, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, poly- to benzene Naphthalate, polymethyl methacrylate, polyimides, aromatic polyamide, cellulose, nitrocotton, NBR (propylene Nitrile-butadiene rubber), fluorubber, ethylene-propylene rubber, Styrene-Butadiene-Styrene Block Copolymer or its hydride, EPDM (ethylene-propylene-diene terpolymer), styrene ethylene butadiene-ethylene copolymer, styrene-isoprene- Styrene block copolymer or its hydride, rule -1,2- polybutadiene, polyvinyl acetate, ethylene-vinyl acetate c Object, fluoro polyvinylidene fluoride, tetrafluoroethylene-ethylene copolymer, has alkali metal ion (especially at propylene-alpha-olefin copolymers Lithium ion) ionic conductivity polymeric composition etc..In addition, these substances can be used alone a kind, it also can be with arbitrary Combination and ratio are used in combination of two or more.

About the content of binder, the ratio of the binder in layer as a positive electrode active material, usually 0.1 mass % with On, preferably 1 mass % or more, further preferably 1.5 mass % or more；Also, usually 80 mass % are hereinafter, preferably 60 mass % hereinafter, further preferably 40 mass % hereinafter, most preferably 10 mass % or less.If the ratio mistake of binder Low, then positive mechanical strength may be insufficient, and cannot sufficiently keep positive active material, may make the batteries such as cycle characteristics Penalty.On the other hand, if it is excessively high, cause the reduction of battery capacity, electric conductivity sometimes.

It as above-mentioned thickener, can enumerate: carboxymethyl cellulose, methylcellulose, hydroxymethyl cellulose, ethyl cellulose Element, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein and their salt etc..It can be used alone a kind, it also can be with any Combination and ratio be used in combination of two or more.

The ratio of thickener relative to active material is usually 0.1 mass % or more, preferably 0.2 mass % or more, More preferably 0.3 mass % or more；Also, usually 5 mass % hereinafter, preferably 3 mass % hereinafter, more preferably 2 matter Measure % range below.If being lower than the range, coating may be significantly reduced.If being higher than the range, there may be just Between the problem of ratio shared by active material reduces in the active material layer of pole, the capacity of battery reduces, positive active material Resistance increase the problem of.

As above-mentioned conductive material, well known conductive material can be arbitrarily used.It as specific example, can enumerate: copper, nickel etc. Metal material；The graphite such as natural graphite, artificial graphite (graphite), the carbon blacks such as acetylene carbon black, amorphous carbon such as needle coke etc. Carbon material etc..It, also can in any combination and ratio is used in combination of two or more in addition, they can be used alone a kind.Positive-active Conductive material is usually 0.01 mass % or more, preferably 0.1 mass % or more, more preferably 1 mass % or more in material layer； Also, usually by containing 50 mass % or less, preferably 30 mass % or less, more preferably 15 mass % it is below in a manner of make With.If content is lower than the range, electric conductivity may be inadequate.Conversely, battery capacity may if content is higher than the range It reduces.

As the solvent for being used to form slurry, as long as positive active material, conductive material, binder, Yi Jigen can be made According to the solvent for needing thickener to be used dissolution or dispersion, then the kind thereof is not particularly limited, can be used water solvent with it is organic Any one in series solvent.As water solvent, such as the mixed solvent etc. of water and alcohol and water can be enumerated.As organic Series solvent, such as can enumerate: the fat hydrocarbons such as hexane；The aromatic hydrocarbons such as benzene,toluene,xylene, methyl naphthalene；Quinoline, pyridine etc. are miscellaneous Cycle compound；The ketones such as acetone, methyl ethyl ketone, cyclohexanone；The esters such as methyl acetate, methyl acrylate；Diethylenetriamines, The amines such as N, N- dimethylamino propylamine；The ethers such as Anaesthetie Ether, propylene oxide, tetrahydrofuran (THF)；N-Methyl pyrrolidone (NMP), the amides such as dimethylformamide, dimethyl acetamide；The aprotic polars such as hexamethyl phosphoramide, dimethyl sulfoxide Solvent etc..

It as the material of positive collector, can enumerate: the metals such as the metals such as aluminium, titanium, tantalum, stainless steel, nickel or its alloy Material；The carbon materials such as carbon cloth, carbon paper.Wherein, preferred metal materials, especially aluminium or its alloy.

As the shape of collector, in the case where metal material, metal foil, metal cylinder, wire coil, gold can be enumerated Belong to plate, metallic film, net form metal (expanded metal), punch metal plate, foaming metal etc.；In the case where carbon material, Carbon plate, C film, carbon cylinder etc. can be enumerated.Among them, preferred metallic film.In addition, it is netted that film, which can also be suitably formed,. Film with a thickness of any, usually 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more；Also, usually 1mm with Under, preferably 100 μm hereinafter, more preferably 50 μm or less.It, can as intensity needed for collector if film is thinner than the range Energy can be inadequate.Conversely, operability may be damaged if film is thicker than the range.

In addition, from the viewpoint of the contact resistance for reducing collector and positive electrode active material layer, it is also preferred that in collector Surface be coated with conductive auxiliary agent.As conductive auxiliary agent, the precious metals such as carbon, gold, platinum, silver can be enumerated.

The ratio between collector and the thickness of positive electrode active material layer are not particularly limited, and still, (will carry out injecting electrolytic solution When single side positive electrode active material layer thickness)/the value of (thickness of collector) be preferably 20 or less, more preferably 15 with Under, be most preferably 10 ranges below；And preferably 0.5 or more, it is more preferably the model of 0.8 or more, most preferably 1 or more It encloses.If being higher than the range, when high current density charge and discharge collector may cause of occurrence in the fever of Joule heat.If lower than should Range, then collector increases relative to the volume ratio of positive active material, and the capacity of battery may be reduced.

The manufacture of anode is according to conventional methods.Such as following methods can be enumerated: added in Xiang Shangshu positive active material Enter above-mentioned binder, thickener, conductive material, solvent etc., the anode mixture of pulp-like be made, it is coated on collector, Compacting is carried out after dry is allowed to densification.

Above-specified high densityization can be carried out using hand press, roll squeezer etc..The density of positive electrode active material layer is preferably 1.5g/cm³Above, it is more preferably 2g/cm³It above, is more preferably 2.2g/cm³Above range；Also, preferably 5g/ cm³Below, it is more preferably 4.5g/cm³It below, is more preferably 4g/cm³Range below.If being higher than the range, it is electrolysed Permeability of the liquid near collector/reactive species interface may reduce, especially the charge-discharge characteristic under high current density It may reduce thus cannot get high output.In addition, the electric conductivity between active material may drop if being lower than above range Low, cell resistance may increase thus cannot get high output.

When using electrolyte of the invention, from the viewpoint of stability when improving high output and high temperature, preferably make The area of positive electrode active material layer is big relative to the external surface area of battery external shell.Specifically, positive electrode area is total 15 times or more are preferably set in terms of area ratio with the surface area of the exterior to secondary cell, be more preferably further set as 40 times with On.In the case where there is bottom square shape, the external surface area of battery exterior shell refer to by filled with except terminal protrusion with The longitudinal direction of the housing parts of outer generating element and the gross area for laterally being calculated and being sought with the size of thickness.There is bottom circle In the case where barrel shape, the external surface area of battery exterior shell refers to the generating element that will be filled in addition to the protrusion of terminal The geometrical surface that obtains when being approximately cylinder of housing parts.The summation of the electrode area of anode refers to and contains negative electrode active The geometrical surface of the opposite positive electrode material mixture layer of the mixture layer of substance, clip current collector foil two sides formed positive electrode material mixture layer and In the structure obtained, refer to the summation of the area calculated respectively to each face.

The thickness of positive plate is not particularly limited, and still, from the viewpoint of high capacity and high output, has deducted core material gold The thickness for belonging to the mixture layer of the thickness of foil is preferably 10 μm or more, more preferably 20 μm as lower limit for the single side of collector More than；Also, preferably 500 μm or less, more preferably 450 μm or less.

In addition, the surface that can be used on above-mentioned positive plate is attached with knot obtained from the substance of different composition Structure.As surface attachment, can enumerate: aluminium oxide, silica, titanium oxide, zirconium oxide, magnesia, calcium oxide, boron oxide, The oxides such as antimony oxide, bismuth oxide, the sulfate such as lithium sulfate, sodium sulphate, potassium sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, carbonic acid The carbonate such as lithium, calcium carbonate, magnesium carbonate, carbon, etc..

< cathode >

Cathode is made of the negative electrode active material layer containing negative electrode active material and collector.

As above-mentioned negative electrode active material, can enumerate: the thermal decomposition product of organic matter under the conditions of various thermal decompositions or Artificial graphite, natural graphite etc. can make the carbonaceous material of lithium insertion deintercalation；Tin oxide, silica etc. can make lithium be embedded in deintercalation Metal oxide materials；Lithium metal；Various lithium alloys；Metallic composite oxides material etc. containing lithium.These negative electrode active materials Matter can be mixed with two or more.

As the carbonaceous material that can make lithium insertion deintercalation, preferably by being dripped to the easy graphitization obtained by various raw materials The high-temperature process of green (pitch) is come the artificial graphite or refined natural graphite that manufacture or with organic matters such as pitches to this A little graphite implement material obtained from surface treatment is carbonized later.Selected from following range of material due to initial stage irreversible appearance Amount, the balance of high current density charge-discharge characteristic well, are therefore preferred: to natural graphite, artificial graphite, artificial carbonaceous material And carbonaceous material obtained from the heat treatment that carries out 1 time or more with 400~3200 DEG C of range of artificial graphite metallic substance, make to bear Pole active material layer includes at least two kinds of above to have different crystalline carbonaceous and/or the crystalline carbonaceous of the difference has The carbonaceous material of contact interface makes negative electrode active material layer with contact circle of the carbonaceous of at least two kinds of above different orientations The carbonaceous material in face.In addition, these carbon materials can be used alone a kind, also can in any combination and ratio and with 2 kinds with On.

Artificial carbonaceous material and artificial graphite metallic substance are carried out 1 time with 400~3200 DEG C of range as above-mentioned Carbonaceous material obtained from above heat treatment can be enumerated: coal system coke, petroleum coke, coal system pitch, petroleum drip It is green and carbonaceous material obtained from oxidation processes, needle coke, pitch coke and to their carry out portions are carried out to these pitches The thermal decomposition product of organic matters such as carbon preparation, furnace black, acetylene carbon black, asphalt base carbon fiber obtained by point graphitization can be carbonized Organic matter and their carbide or so that the organic matter that can be carbonized is dissolved in benzene,toluene,xylene, quinoline, n-hexane etc. low Solution obtained from molecule organic solvent and their carbide etc..

As the metal material (except lithium-titanium composite oxide) for being used as above-mentioned negative electrode active material, as long as lithium can be made embedding Enter deintercalation, then lithium simple substance, form lithium alloy elemental metals and alloy or their oxide, carbide, nitride, Any one in the compounds such as silicide, sulfide or phosphide, is not particularly limited.As formation lithium alloy Elemental metals and alloy, the material of the metal semimetallic elements preferably containing 13 races and 14 races, more preferably aluminium, silicon And tin (hereinafter referred to as " special metal element ") elemental metals and alloy or compound containing these atoms.They It can be used alone a kind, it also can in any combination and ratio is used in combination of two or more.

As the negative electrode active material at least one kind of atom in special metal element, can enumerate: any a kind The metal simple-substance of special metal element, the alloy comprising special metal element of more than two kinds, comprising one kind or two or more specific The alloy of metallic element and other one kind or two or more metallic elements and contain one kind or two or more special metal element Compound and the compound the compound chemical combination such as oxide, carbide, nitride, silicide, sulfide or phosphide Object.By by these metal simple-substances, alloy or metallic compound be used as negative electrode active material, it can be achieved that battery high capacity.

In addition, it is complicated to enumerate the several elements such as these complex chemical compounds and metal simple-substance, alloy or nonmetalloid Compound obtained from ground combines.Specifically, such as using silicon, tin, these elements can be used and not as negative The alloy of the metal of pole work.Such as in the case where tin, can be used tin and the metal in addition to silicon as cathode effect, into The complication containing 5~6 kinds of elements as combination with the metal and nonmetalloid that work not as cathode of one step ground Close object.

Specifically, it can enumerate: Si simple substance, SiB₄、SiB₆、Mg₂Si、Ni₂Si、TiSi₂、MoSi₂、CoSi₂、NiSi₂、 CaSi₂、CrSi₂、Cu₆Si、FeSi₂、MnSi₂、NbSi₂、TaSi₂、VSi₂、WSi₂、ZnSi₂、SiC、Si₃N₄、Si₂N₂O、SiO_v(0 V≤2 <), LiSiO or tin simple substance, SnSiO₃、LiSnO、Mg₂Sn、SnO_w(0 w≤2 <).

In addition, can enumerate with Si or Sn as the first component, the in addition to this composite material containing the 2nd, the 3rd component. 2nd component is, for example, at least one kind of in cobalt, iron, magnesium, titanium, vanadium, chromium, manganese, nickel, copper, zinc, gallium and zirconium.3rd composition member Element is, for example, at least one kind of in boron, carbon, aluminium and phosphorus.

Particularly, from the viewpoint of can be obtained high battery capacity and excellent battery behavior, as above-mentioned metal material, It is preferred that silicon or tin simple substance (containing micro impurity), SiO_v(0 v≤2 <), SnO_w(0≤w≤2), Si-Co-C composite material, Si-Ni-C composite material, Sn-Co-C composite material, Sn-Ni-C composite material.

As the metallic composite oxides material containing lithium of negative electrode active material is used as, as long as lithium can be made to be embedded in deintercalation, Then it is not particularly limited.But from the aspect of high current density charge-discharge characteristic, the material of titanium and lithium is preferably comprised, The composite oxides of the further preferably lithium-contained composite metal oxide material of titanium, further preferred lithium and titanium are (hereinafter referred to as " lithium-titanium composite oxide ").That is, when making the lithium-titanium composite oxide with spinel structure be contained in electrolyte battery cathode It in active material and in use, output resistance is greatly reduced, therefore is particularly preferred.

As above-mentioned lithium-titanium composite oxide, preferably by general formula:

Li_xTi_yM_zO₄

The compound of expression.[in formula, M is indicated selected from being made of Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb At least one kind of element in group.]

Among above-mentioned composition, meet

(i) 1.2≤x≤1.4,1.5≤y≤1.7, z=0

(ii) 0.9≤x≤1.1,1.9≤y≤2.1, z=0

(iii) 0.7≤x≤0.9,2.1≤y≤2.3, z=0

Structure since the balance of battery performance is good be particularly preferred.

The particularly preferred representative composition of above compound are as follows: be Li in the case where (i)_4/3Ti_5/3O₄, (ii) feelings It is Li under condition₁Ti₂O₄, be Li in the case where (iii)_4/5Ti_11/5O₄.In addition, the structure about Z ≠ 0, as preferred structural example Li can such as be enumerated_4/3Ti_4/3Al_1/3O₄。

Above-mentioned cathode agent preferably also contains binder, thickener, conductive material.

As above-mentioned binder, binder identical with the above-mentioned binder that can be used for anode can be enumerated.Binder phase Ratio for negative electrode active material is preferably 0.1 mass % or more, further preferably 0.5 mass % or more, particularly preferably For 0.6 mass % or more.Also, preferably 20 mass % hereinafter, more preferably 15 mass % hereinafter, further preferably 10 matter % is measured hereinafter, particularly preferably 8 mass % or less.If binder is higher than above range relative to the ratio of negative electrode active material, The ratio that the binder of battery capacity is then helpless in binder amount increases, sometimes results in battery capacity reduction.In addition, if low In above range, the strength reduction of negative electrode is sometimes resulted in.

Particularly, when containing using SBR as the rubber-like macromolecule of representative as main component, binder is relative to cathode The ratio of active material is usually 0.1 mass % or more, preferably 0.5 mass % or more, further preferably 0.6 mass % with On；Also, usually 8 mass % hereinafter, preferably 5 mass % hereinafter, further preferably 3 mass % or less.In addition, containing When having using polyvinylidene fluoride as the fluorine class macromolecule of representative as main component, ratio of the binder relative to negative electrode active material Example is usually 0.5 mass % or more, preferably 1 mass % or more, further preferably 3 mass % or more；Also, usually 15 Quality % hereinafter, preferably 10 mass % hereinafter, further preferably 8 mass % or less.

As above-mentioned thickener, thickener identical with the above-mentioned thickener that can be used for anode can be enumerated.Thickener phase Ratio for negative electrode active material is usually 0.1 mass % or more, preferably 0.5 mass % or more, and further preferably 0.6 Quality % or more；Also, usually 5 mass % hereinafter, preferably 3 mass % hereinafter, further preferably 2 mass % or less. If thickener is lower than above range relative to the ratio of negative electrode active material, coating is significantly reduced sometimes.In addition, if being higher than Above range, ratio shared by negative electrode active material reduces in negative electrode active material layer, there are problems that battery capacity reduction, negative The case where resistance between the active material of pole increases.

It as the conductive material of cathode, can enumerate: the metal materials such as copper, nickel；Carbon materials such as graphite, carbon black etc..

As the solvent for being used to form slurry, as long as negative electrode active material, binder and used as needed can be made Thickener and the solvent of conductive material dissolution or dispersion, then the kind thereof is not particularly limited, and water solvent and organic system can be used Any one in solvent.

As water solvent, water, alcohol etc. can be enumerated.It as organic solvent, can enumerate: N-Methyl pyrrolidone (NMP), diformazan Base formamide, dimethyl acetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethylenetriamines, N, N- Dimethylamino propylamine, tetrahydrofuran (THF), toluene, acetone, Anaesthetie Ether, dimethyl acetamide, hexamethyl phosphoramide, two Methyl sulfoxide, benzene, dimethylbenzene, quinoline, pyridine, methyl naphthalene, hexane etc.

As the material of cathode collector, copper, nickel or stainless steel etc. can be enumerated.Wherein, from being easily worked as film Aspect and cost from the aspect of, preferred copper foil.

The thickness of collector is usually 1 μm or more, and preferably 5 μm or more；Usually 100 μm hereinafter, preferably 50 μm with Under.If the thickness of negative electrode collector is blocked up, the capacity of battery entirety is excessively reduced sometimes；Conversely, being not easy sometimes if excessively thin Operation.

The manufacture of cathode is according to conventional methods.Such as following methods can be enumerated: be added in Xiang Shangshu negative electrode material Binder, thickener, conductive material, solvent for stating etc., are made pulp-like, are coated on collector, are suppressed after dry, is high It is densification.In addition, when using alloy material, it is possible to use formed using gimmicks such as vapour deposition method, sputtering method, plating methods containing upper The method for stating the film layer (negative electrode active material layer) of negative electrode active material.

Electrode structure when by negative electrode active material electric polarization is not particularly limited, and still, is present in negative on collector The density of pole active material is preferably 1gcm^-3More than, further preferably 1.2gcm^-3More than, particularly preferably 1.3g cm^-3More than；Also, preferably 4.0gcm^-3Hereinafter, more preferably 3.0gcm^-3Hereinafter, further preferably 2.5gcm^-3 Hereinafter, particularly preferably 1.9gcm^-3Below.It is present in the density of the negative electrode active material on collector if more than above-mentioned model It encloses, then negative electrode active material particle is destroyed sometimes, leads to the increase of initial stage irreversible capacity, because electrolyte is to collector/negative The deterioration of high current density charge-discharge characteristic caused by permeability near the reactive species interface of pole reduces.In addition, if being less than upper Range is stated, then the electric conductivity between negative electrode active material reduces sometimes, cell resistance increases, the capacity of per unit volume reduces.

The thickness of negative plate cooperates used positive plate and designs, and is not particularly limited, but it is desirable to having deducted core material The thickness of the mixture layer of the thickness of metal foil is usually 15 μm or more, preferably 20 μm or more, more preferably 30 μm or more；And And usually 300 μm hereinafter, preferably 280 μm hereinafter, more preferably 250 μm or less.

In addition, the surface that can be used on above-mentioned negative plate is attached with knot obtained from the substance of different composition Structure.As surface attachment, can enumerate: aluminium oxide, silica, titanium oxide, zirconium oxide, magnesia, calcium oxide, boron oxide, The oxides such as antimony oxide, bismuth oxide, the sulfate such as lithium sulfate, sodium sulphate, potassium sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, carbonic acid Carbonate such as lithium, calcium carbonate, magnesium carbonate etc..

< diaphragm >

Lithium ion secondary battery of the invention is preferably also equipped with diaphragm.

Material, the shape of above-mentioned diaphragm are not particularly limited as long as and liquid retention stable to electrolyte is excellent, and public affairs can be used The diaphragm known.Wherein, it is preferable to use by the stable material of electrolyte of the invention formed (can be used resin, glass fibre, Inorganic matter etc.), the excellent porous sheet or the diaphragm of non-woven fabric-like form of liquid retention etc..

As resin, the material of fibreglass diaphragm, such as the polyolefin such as polyethylene, polypropylene, fragrant adoption can be used Amide, polytetrafluoroethylene (PTFE), polyether sulfone, glass filters etc..3 layers of 2 tunic of polypropylene, polyethylene, polypropylene, polyethylene/polypropylene Film etc., these materials can be used alone a kind, also can in any combination and ratio is used in combination of two or more.Wherein, from electrolyte Permeability, shutdown (shutdown) work well from the aspect of, above-mentioned diaphragm preferably with polyenes such as polyethylene, polypropylene Hydrocarbon is porous sheet or non-woven fabrics of raw material etc..

Diaphragm with a thickness of any, but usually 1 μm or more, preferably 5 μm or more, further preferably 8 μm or more；And And usually 50 μm hereinafter, preferably 40 μm hereinafter, further preferably 30 μm or less.If diaphragm is excessively thinner than above range, Then insulating properties, mechanical strength reduce sometimes.In addition, not only the battery performances such as multiplying power property can if excessively thicker than above range It can reduce, and the energy density as electrolyte battery entirety may reduce.

Further, in the case where using the porous materials such as porous sheet, non-woven fabrics as diaphragm, the hole of diaphragm Gap rate is arbitrary, but usually 20% or more, and preferably 35% or more, further preferably 45% or more；Also, it is usually 90% hereinafter, preferably 85% hereinafter, further preferably 75% or less.If porosity is excessively smaller than above range, exist The trend that film resistance increases, multiplying power property deteriorates.In addition, there are the mechanical strength of diaphragm drops if excessively bigger than above range The trend that low, insulating properties reduces.

In addition, the average pore size of diaphragm is also arbitrary, but usually 0.5 μm hereinafter, preferably 0.2 μm or less；Also, Usually 0.05 μm or more.Average pore size is then easy to happen short circuit if more than above range.In addition, if being less than above range, Sometimes film resistance increases, multiplying power property reduces.

On the other hand, as inorganic material, such as the oxides such as aluminium oxide, silica, aluminium nitride, nitridation can be used The nitride such as silicon, the sulfate such as barium sulfate, calcium sulfate；The material of shape of particle or fiber shape can be used.

As form, the material of the thin film shapes such as non-woven fabrics, woven cloths, micro- porous membrane can be used.Among thin film shape, It the use of aperture is preferably 0.01~1 μm, with a thickness of 5~50 μm of shapes.In addition to above-mentioned independent thin film shape, may be used also Composite porous layer containing above-mentioned inorganic particles is formed in the table of anode and/or cathode using the binder using resin Diaphragm obtained from layer.Such as can enumerate anode two sides fluororesin make oxidation of 90% partial size less than 1 μm as binder Aluminum particulate forms porous layer.

< battery design >

Electrode group can be above-mentioned diaphragm is clipped between above-mentioned positive plate and negative plate and the electrode group of the stepped construction that is formed, with And clipped between above-mentioned positive plate and negative plate above-mentioned membrane winding it is spiral obtained from structure electrode group in it is any One.The volume of electrode group proportion (hereinafter referred to as electrode group occupancy rate) in battery content is usually 40% or more, Preferably 50% or more；Also, usually 90% hereinafter, preferably 80% or less.

If electrode group occupancy rate is lower than above range, battery capacity becomes smaller.In addition, if being higher than above range, gap Space is small, and since battery becomes high temperature, component expands, the vapour pressure of the liquid component of electrolyte gets higher and makes internal pressure Rise, there is that the various characteristics such as the repeated charge performance as battery, High temperature storage reduce or further make will be internal Pressure is discharged into the case where external gas release valve starts.

Current collecting is not particularly limited, still, in order to more effectively realize by the high electricity of electrolyte bring of the invention The raising of the charge-discharge characteristic of current density is preferably formed as reducing the structure of the resistance of wiring part, coupling part.In this reduction In the case where internal resistance, the effect using electrolyte of the invention will be particularly good played.

, it is preferable to use the metal core portion bundle of each electrode layer is welded in terminal in the electrode group of above-mentioned stepped construction The structure of formation.When the area of a plate electrode is big, because internal resistance is big, it is also preferred that multiple terminals are arranged in electrode makes electricity Resistance reduces.In the electrode group of above-mentioned winding-structure, multiple pin configurations are respectively set in anode and cathode and are bundled it In terminal, internal resistance thus can be reduced.

As long as the material of the external shell substance stable to used electrolyte is then not particularly limited.Specifically, Stacked film (the lamination of the metals classes such as nickel-clad steel plate, stainless steel, aluminum or aluminum alloy, magnesium alloy or resin and aluminium foil can be used Film)., it is preferable to use aluminum or aluminum alloy metal, laminated film from the viewpoint of lightweight.

In the external shell using metal class, it can enumerate each gold using laser welding, resistance welding, ultrasonic bonding Belong to weldering to connect, form the external shell of enclosed structure or forms filleting (か via the above-mentioned metal class of resin washer め) the external shell of structure.In the external shell for stating laminated film in use, can enumerate by by each resin layer thermal welding come shape At the external shell etc. of enclosed structure.For lift-off seal, can be mingled between above-mentioned resin layer is made with laminated film The different resin of resin.Particularly, in the case where clipping current-collecting terminals for resin layer thermal welding formation sealing structure, by In the connection for forming metal and resin, therefore, as the resin being mingled with, it is preferable to use there is the resin of polar group, be imported with The modified resin of polar group.

The shape of lithium ion secondary battery of the invention is arbitrary, and it can be mentioned, for example cylinder types, angle-style, laminated-type, hard The shapes such as coin type, large size.In addition, the shape and composition of anode, cathode, diaphragm can be changed according to the shape of various batteries come It uses.

In addition, the component for having lithium ion secondary battery of the invention is also one aspect of the present invention.

Above-mentioned lithium ion secondary battery can also have anode, cathode and above-mentioned electrolyte；Above-mentioned anode has positive collection Electric body and positive electrode active material layer containing positive active material；Above-mentioned positive active material contains Mn.By have containing The positive electrode active material layer of positive active material containing Mn, above-mentioned lithium ion secondary battery are more excellent in terms of High temperature storage characteristic It is different.

As above-mentioned positive active material, can enumerate by formula: Li_aMn_2-bM¹ _bO₄The lithium manganese spinel combined oxidation of expression Object (in formula, 0.9≤a；0≤b≤1.5；M¹For selected from by Fe, Co, Ni, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, At least one kind of metal in the group of Ga, In, Si and Ge composition).

Wherein, from the viewpoint of the lithium ion secondary battery that can provide high, the high output of energy density, preferably LiNi_0.5Mn_1.5O₄、LiMnO₂、LiMn₂O₄、LiNi_1/3Co_1/3Mn_1/3O₂、Li_1.2Fe_0.4Mn_0.4O₂And LiNi_0.5Mn_0.5O₂。

The content of above-mentioned positive active material in positive electrode active material layer is preferably 80 mass % or more, and more preferably 82 Quality % or more, particularly preferably 84 mass % or more.Also, the upper limit is preferably 99 mass %, more preferably 98 mass %.If The content of positive active material in positive electrode active material layer is low, then capacitance may be insufficient.Conversely, if too high levels, just The intensity of pole may be insufficient.

Above-mentioned positive electrode active material layer can also contain conductive material, thickener and binder.

As above-mentioned binder, as long as used solvent, electrolyte safety when to manufacture electrode, may be used arbitrary Material, such as can enumerate: polyvinylidene fluoride, polytetrafluoroethylene (PTFE), polyethylene, polypropylene, SBR (SBR styrene butadiene rubbers), Isoprene rubber, butadiene rubber, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, poly terephthalic acid Glycol ester, polymethyl methacrylate, polyimides, aromatic polyamide, cellulose, nitrocotton, NBR (acrylic nitrile-butadiene two Alkene rubber), fluorubber, ethylene-propylene rubber, Styrene-Butadiene-Styrene Block Copolymer or its hydride, EPDM (second Alkene-propylenediene terpolymer), styrene ethylene butadiene-ethylene copolymer, styrene-isoprene-phenylethene Block copolymer or its hydride, rule -1,2- polybutadiene, polyvinyl acetate, vinyl-vinyl acetate copolymer, third Alkene-alpha olefin copolymer, tetrafluoroethylene-ethylene copolymer, has alkali metal ion (especially lithium at fluoro polyvinylidene fluoride Ion) ionic conductivity polymeric composition etc..In addition, these substances can be used alone a kind, it also can be in any combination And ratio is used in combination of two or more.

About the content of binder, the ratio of the binder in layer as a positive electrode active material, usually 0.1 mass % with On, preferably 1 mass % or more, further preferably 1.5 mass % or more；Also, usually 80 mass % are hereinafter, preferably 60 mass % hereinafter, further preferably 40 mass % hereinafter, most preferably 10 mass % or less.If the ratio mistake of binder Low, then positive mechanical strength may be insufficient, cannot sufficiently be kept to positive active material, and cycle characteristics etc. is cell performance It can may deteriorate.On the other hand, if it is excessively high, it may result in battery capacity, electric conductivity reduces.

As above-mentioned thickener, can enumerate carboxymethyl cellulose, methylcellulose, hydroxymethyl cellulose, ethyl cellulose, Polyvinyl alcohol, oxidized starch, phosphorylated starch, casein and their salt etc..It can be used alone a kind, it also can be with arbitrary Combination and ratio are used in combination of two or more.

Thickener is usually 0.1 mass % or more, preferably 0.2 mass % or more, more relative to the ratio of active material The preferably range of 0.3 mass % or more；Also, usually 5 mass % or less, preferably 3 mass % or less, more preferably 2 Quality % range below.If being lower than the range, the case where there are coating significant decreases.If being higher than the range, activity The ratio that substance accounts for positive electrode active material layer reduces, and may lead to the problem of battery capacity reduces, between positive active material Resistance increase the problem of.

As above-mentioned conductive material, well known conductive material can be arbitrarily used.It as specific example, can enumerate: copper, nickel etc. Metal material, the graphite such as natural graphite, artificial graphite (Graphite), the carbon blacks such as acetylene carbon black, amorphous carbon such as needle coke etc. Carbon material etc..It, also can in any combination and ratio is used in combination of two or more in addition, they can be used alone a kind.Conductive material In positive electrode active material layer be usually 0.01 mass % or more, preferably 0.1 mass % or more, more preferably 1 mass % with On；Also, usually to make containing 50 mass % or less, preferably 30 mass % or less, more preferably 15 mass % amounts below With.If content is lower than the range, electric conductivity may be insufficient.If battery capacity may conversely, content is higher than the range It can reduce.

From the viewpoint of further improving High temperature storage characteristic, preferably above-mentioned positive electrode collector is by valve metal or its conjunction Gold is constituted.As above-mentioned valve metal, aluminium, titanium, tantalum, chromium etc. can be enumerated.More preferable above-mentioned positive electrode collector is by aluminum or aluminum alloy structure At.

From the viewpoint of further improve High temperature storage characteristic, preferably above-mentioned lithium ion secondary battery with it is above-mentioned just It is also made of valve metal or its alloy in the part of electrode current collector electrical connection with the part of electrolyte contacts.In particular it is preferred to electric Be electrically connected among pond external shell and the lead, the safety valve that are contained in above-mentioned battery external shell etc. with positive electrode collector and The part contacted with nonaqueous electrolytic solution is made of valve metal or its alloy.It can also be used by the stainless of valve metal or its alloy-coated Steel.

The manufacturing method of above-mentioned anode with it is mentioned-above identical, such as following methods can be enumerated: Xiang Shangshu positive-active Above-mentioned binder, thickener, conductive material, solvent etc. are added in substance, the anode mixture of pulp-like is made, by coating with it is upper It states on positive electrode collector, is suppressed after dry, densification.

The composition of above-mentioned cathode with it is mentioned-above identical.

Above-mentioned double layer capacitor can have anode, cathode and above-mentioned electrolyte.

In above-mentioned double layer capacitor, anode and cathode at least 1 be polarizability electrode, as polarizability electrode with And non-polarized property electrode, the following electrode being disclosed in detail in Japanese Unexamined Patent Publication 9-7896 bulletin can be used.

Polarizability electrode used in the present invention based on active carbon preferably comprises the not active carbon of bigger serface With the conductive agents such as the carbon black that imparts electron conduction.Polarizability electrode can be formed by various methods.For example, by active powdered carbon End, carbon black and phenolic aldehyde system resin mixing, are burnt in non-active gas atmosphere and in steam atmosphere after compression moulding At, activation, thus can form the polarizability electrode containing active carbon and carbon black.It is preferred that the polarizability electrode is binded using electric conductivity Agent etc. is bonded with collector.

It is configured to sheet in addition, can also mediate in the presence of an alcohol active carbon powder, carbon black and bonding agent, is done It is dry, form polarizability electrode.For the bonding agent, such as polytetrafluoroethylene (PTFE) can be used.In addition, can also be by active carbon powder, charcoal Black, bonding agent and solvent are mixed and made into slurry, which is covered in collector metal foil, is dried, and are formed and are collected The electric integrated polarizability electrode of body.

The polarizability electrode based on active carbon can be used to form double layer capacitor but it is also possible to be in list at the two poles of the earth Side uses the composition of non-polarized property electrode, such as can be and be combined with based on the cell active materials such as metal oxide just Formed obtained from pole and cathode as the polarizability electrode based on active carbon, be also possible to be combined with can make lithium from Cathode or lithium metal, lithium alloy cathode based on the sub carbon material for being reversibly embedded in, being detached from and the pole based on active carbon It is formed obtained from the property changed anode.

In addition, it is possible to use the carbonaceous such as carbon black, graphite, expanded graphite, porous carbon, carbon nanotube, carbon nanohorn, Ketjen black Material replaces active carbon or is used in combination therewith.

As non-polarized property electrode, preferably by based on lithium ion can be made reversibly to be embedded in, be detached from carbon material and The material obtained after lithium ion is embedded in the carbon material for electrode.At this point, lithium salts can be used in electrolyte.According to the double of the composition Electric layer capacitor, can be obtained it is higher be more than 4V proof voltage.

Solvent used in the preparation of slurry in electrode fabrication is preferably the solvent for dissolving bonding agent, according to bonding agent Type can suitably select N-Methyl pyrrolidone, dimethylformamide, toluene, dimethylbenzene, isophorone, methyl ethyl ketone, second Acetoacetic ester, methyl acetate, repefral, ethyl alcohol, methanol, butanol or water.

As active carbon used in polarizability electrode, there are phenolic resin system active carbon, coconut husk class active carbon, petroleum coke It is active carbon etc..Among them, it is preferable to use petroleum coke system active carbon or phenolic aldehyde tree from the aspect of large capacity can be obtained Rouge system active carbon.In addition, the activation processing method of active carbon has steam-activation treatment method, melting KOH activation processing method etc., from can It obtains from the aspect of bigger capacity, it is preferable to use being activated the active carbon that method obtains using melting KOH.

As preferred conductive agent used in polarizability electrode, carbon black, Ketjen black, acetylene carbon black, natural stone can be enumerated Ink, artificial graphite, metallic fiber, electric conductivity titanium oxide, ruthenium-oxide.Good electric conductivity (low internal resistance) in order to obtain, and by Reduce in the capacity of the product if excessive, therefore, the combined amounts of the conductive agents such as carbon black used in polarizability electrode with activity It is preferably 1~50 mass % in the total amount of charcoal.

In addition, as active carbon used in polarizability electrode, large capacity and the electric double layer capacitance of low internal resistance in order to obtain Device is, it is preferable to use average grain diameter is 20 μm or less and specific surface area is 1500~3000m²The active carbon of/g.In addition, as being used for The preferred carbon material for constituting the electrode based on lithium ion can be made reversibly be embedded in, be detached from carbon material can be enumerated naturally Graphite, artificial graphite, graphitized intermediate-phase carbosphere, graphitization whisker, gas-phase growth of carbon fibre, furfuryl alcohol resin firing product or The firing product of Novolak resin.

As long as collector has chemistry, electrochemistry corrosion resistance.As the polarizability electrode based on active carbon Collector, preferably use stainless steel, aluminium, titanium or tantalum.Among them, stainless steel or aluminium are in obtained double layer capacitor Characteristic and price two in terms of be particularly preferred material.As the carbon material lithium ion can be made reversibly to be embedded in, be detached from The collector of the electrode of main body is, it is preferable to use stainless steel, copper or nickel.

In addition, for being embedded in lithium ion in advance into the carbon material that lithium ion can be made reversibly to be embedded in, be detached from, just like lower section Method: (1) powdered lithium is made to be mixed into the method for carbon material that lithium ion can be made reversibly to be embedded in, be detached from；(2) it is placed by lithium foil On the electrode that the carbon material and bonding agent that Yu Youneng is embedded in lithium ion reversibly, is detached from are formed and make lithium foil and electrode electrical contact In the state of, it is impregnated in the electrode in the electrolyte for having dissolved lithium salts, thus makes lithium ion, lithium ion is made to enter carbon material In method；(3) by by lithium ion can be made reversibly to be embedded in, be detached from carbon material and the electrode that is formed of bonding agent be placed in negative side, Lithium metal is placed in positive side, is impregnated in the non-aqueous electrolyte using lithium salts as electrolyte, makes electric current flowing, thus with electricity The method that the mode of chemistry enters lithium in the state of ionization in carbon material.

As double layer capacitor, commonly known winding-type double layer capacitor, laminated-type double layer capacitor, Coin shape Double layer capacitor etc., above-mentioned double layer capacitor can also be set as these forms.

Such as winding-type double layer capacitor, can by the anode of the laminated body (electrode) comprising collector and electrode layer and Cathode clips diaphragm and is wound to make winding element, which is put into the shells such as aluminum, fills up electrolyte, preferably Close encapsulation is carried out with the seal body of rubber system, is thus assembled thereafter for non-aqueous electrolyte.

As diaphragm, the diaphragm of known material and composition can be used.Such as it can enumerate: polyethylene porous plasma membrane, Polypropylene fibre, glass fibre, cellulose fibre non-woven fabrics etc..

In addition, can also be formed according to well known method and carry out the anode of sheet and cathode across electrolyte and diaphragm Laminated-type double layer capacitor obtained from stacking, by anode and cathode be fixed with gasket and across electrolyte and every Film constitutes coin type electric double layer obtained from Coin shape.

The large-scale lithium ion secondary battery electricity consumption of electrolyte of the invention as Hybrid Vehicle, distributed generation resource Solve liquid, electrolyte solution for electric double layer capacitor is useful.

Embodiment

In the following, enumerating, examples illustrate the present invention, but the present invention is not only limited to the embodiment.

Embodiment and comparative example documented by table 1 and table 2

(preparation of electrolyte)

Each component is mixed with the ratio relative to electrolyte and is formed documented by table 1 and table 2 with becoming, is added thereto Add LiPF₆To become the concentration of 1.0 mol/Ls, nonaqueous electrolytic solution is obtained.

Compound in table is as follows.

Component (A)

[changing 112]

Component (B)

[changing 113]

Component (C)

[changing 114]

[changing 115]

[changing 116]

[changing 117]

[changing 118]

[changing 119]

Other components

EP: ethyl propionate

EMC: methyl ethyl carbonate

EC: ethylene carbonate

PC: propylene carbonate

(production of Coin shape lithium ion secondary battery)

Use LiNi_1/3Mn_1/3Co_1/3O₂As a positive electrode active material, it uses carbon black as conductive material, use polyvinylidene fluoride (PVdF) n-methyl-2-pyrrolidone dispersion is as binder, with the solid of active material, conductive material and binder The mode that ingredient ratio becomes 92/3/5 (quality % ratio) is mixed, and anode mixture slurry is thus prepared for.By it is obtained just Pole mix paste is equably coated on the aluminium foil collector with a thickness of 20 μm, after being dried, is pressed using press It shortens shape into, forms anode.Positive laminated body is punched to the size of diameter 1.6cm with punching machine, the anode of round shape is made.

Use artificial powdered graphite as negative electrode active material, (carboxymethyl is fine with the water-borne dispersions of sodium carboxymethylcellulose The concentration for tieing up plain sodium is 1 mass %) as thickener, with water-borne dispersions (styrene-fourth two of SBR styrene butadiene rubbers The concentration of alkene rubber is 50 mass %) it is used as binder, become with the solid component ratio of active material, thickener and binder 97.6/1.2/1.2 the mode of (quality % ratio) is mixed into pulp-like in aqueous solvent, is thus prepared for cathode agent slurry.? It is coated on the copper foil with a thickness of 20 μm evenly, after dry, carry out compression molding using press, form cathode.Use punching machine It is punched to the size of diameter 1.6cm, the cathode of round shape is made.

Make the anode of above-mentioned round shape across the microporous polyethylene film (diaphragm) with a thickness of 20 μm, makes positive electrode and negative electrode phase It is right, injection by nonaqueous electrolytic solution obtained above, in electrolyte full penetration to diaphragm etc. after, close, be pre-charged, always Change, the lithium ion secondary battery of Coin shape is made.

(measurement of battery behavior)

For obtained Coin shape lithium ion secondary battery, residual capacity rate and resistance increment rate are carried out by following main points Research.

(residual capacity rate)

To the secondary cell made of above-mentioned, constant current-constant-voltage charge (following note is carried out to be equivalent to the electric current of 0.5C at 25 DEG C For CC/CV charging) after (0.1C cutting) to 4.4V, with the constant-current discharge to 3V of 0.5C until, using it as 1 circulation, by The discharge capacity of 3rd circulation finds out initial stage discharge capacity.Herein, 1C indicates the electricity that the reference capacity of battery discharges 1 hour Flow valuve, such as 0.5C indicate its 1/2 current value.Again carry out CC/CV charging (0.1C cutting) to 4.4V after, 85 DEG C, High temperature storage is carried out under conditions of 36 hours.Battery after preservation is discharged into 3V at 25 DEG C with 0.5C, with electric discharge appearance Amount is used as residual capacity.

Measure High temperature storage after residual capacity, seek ratio of the residual capacity relative to initial stage discharge capacity, by conduct Residual capacity rate (%).

(residual capacity)/(initial stage discharge capacity) × 100=residual capacity rate (%)

(resistance increment rate)

It will (charging to charging current at 0.5C with defined voltage becomes 0.1C, is being equivalent in defined charge and discharge electric condition Be discharged to 3.0V under the electric current of 1C) under the charge and discharge cycles that carry out recycled as 1, determine resistance after 3 circulations with Resistance after High temperature storage test.Measuring temperature is set as 25 DEG C.The resistance increment rate after food preservation test is found out according to the following formula. Resistance calculates as follows.

The resistance (Ω) × 100 after resistance (Ω)/3 circulation after resistance increment rate (%)=High temperature storage test

(preservation of electrolyte)

After electrolyte obtained is enclosed stainless steel cylinder, saved under 65 DEG C of environment using high temperature slot 14 days (336 hours), it will As save after electrolyte, to electrolyte save after battery behavior evaluate.

(battery behavior after electrolyte preservation)

For having used the electrolyte after saving under the above conditions, the Coin shape lithium ion according to made from above-mentioned production method Secondary cell studies residual capacity rate and resistance increment rate.

[table 1]

[table 2]

Embodiment documented by table 3 and comparative example

(preparation of electrolyte)

Each component is mixed with the ratio relative to electrolyte and is formed documented by table 3 with becoming, adds LiPF thereto₆ To become the concentration of 1.0 mol/Ls, nonaqueous electrolytic solution is obtained.

(production of Coin shape lithium ion secondary battery)

Use Li₂MnO₃As a positive electrode active material, use carbon black as conductive material, with the N- first of polyvinylidene fluoride (PVdF) Base -2-Pyrrolidone dispersion gets out the solid component ratio with active material, conductive material and binder as binder The anode mixture slurry that mode as 90/4/6 (quality % ratio) is obtained by mixing.By obtained anode mixture slurry It is equably coated on the aluminium foil collector with a thickness of 20 μm, after dry, carry out compression molding with press, form anode. Positive laminated body is punched to the size of diameter 1.6cm with punching machine, the anode of round shape is made.

In addition, being added into artificial graphite powder to distill the SBR styrene butadiene rubbers of water dispersion so that it is by solid Ingredient meter becomes 6 mass %, is mixed and is formed as the substance of pulp-like with dispersion machine, it is equably coated on to cathode collection It on electric body (copper foil with a thickness of 10 μm), is dried, forms anode mixture layer.Thereafter, compression molding is carried out using roll squeezer, It is punched to the size of diameter 1.6cm with punching machine, the cathode of round shape is made.

Make the anode of above-mentioned round shape across the microporous polyethylene film (diaphragm) with a thickness of 20 μm, makes positive electrode and negative electrode phase It is right, it injects by nonaqueous electrolytic solution obtained above, after electrolyte is thoroughly impregnated into diaphragm etc., closing is pre-charged, always Change, the lithium ion secondary battery of Coin shape is made.

(measurement of battery behavior)

For obtained Coin shape lithium ion secondary battery, other than charging voltage is changed to 4.6V from 4.4V, with The identical main points of embodiment documented by table 1 and table 2 study residual capacity rate and resistance increment rate.In addition, with Following main points study oxidative resistance.

(oxidative resistance)

(measurement of potential window)

To 3 electric pole type voltage determination battery (working electrodes: platinum；To electrode: Li；Reference electrode: Li.Precious Izumi Ltd. HS Battery) in be put by nonaqueous electrolytic solution obtained above, electric potential scanning is carried out with 5mV/sec with voltage-stablizer at 25 DEG C, measure Electric current (Linear Scan Voltammetric Determination: LSV measurement) is decomposed out.Current value is shown into 1mA/cm²Voltage as decomposition point.

[table 3]

Claims

1. a kind of electrolyte, which is characterized in that contain:

By general formula (1): R¹¹CFX¹¹(CH₂)_n11COOR¹²The compound (1) of expression, in formula, R¹¹For-H ,-F, carbon atom number be 1~ The fluoro-alkyl that 3 non-fluoro-alkyl or carbon atom number is 1~3, X¹¹For-H or-F, R¹²It is not 1~3 not for carbon atom number The fluoro-alkyl that fluoro-alkyl or carbon atom number are 1~3, the integer that n11 is 0~3,

Fluoro carbonic ester and

Selected from by having additive (II), general formula represented by the additive (I) of the structure represented by leading to formula (I), logical formula (II) (III) additive (III) represented by, the additive (IV) with structure represented by any one in logical formula (IV), with And at least one kind of additive in the group of additive represented by logical formula (V) (V) composition；

Logical formula (I):

[changing 1]

Logical formula (II):

[changing 2]

In formula, X¹³~X¹⁶It is identical or different, respectively indicate-H ,-CH₃,-F, the fluoro-alkyl with or without ehter bond or Fluoroalkyl with or without ehter bond；Wherein, X¹³~X¹⁶In at least one be-F, the fluorine with or without ehter bond Substituted alkyl or fluoroalkyl with or without ehter bond；

Logical formula (III):

[changing 3]

In formula, X¹⁷And X¹⁸It is identical or different, respectively indicate-H ,-CH₃,-F, the fluoro-alkyl with or without ehter bond or Fluoroalkyl of the person with or without ehter bond；Wherein, X¹⁷And X¹⁸In any one for-F, with or without ether The fluoro-alkyl of key or fluoroalkyl with or without ehter bond；

Logical formula (IV):

Structure represented by any one in-C ≡ N ,-N=C=O and following [changing 4], [changing 5] and [changing 6]；

[changing 4]

[changing 5]

[changing 6]

Logical formula (V):

[changing 7]

In formula,

A^a+For metal ion, hydrogen ion or ion, the integer that a is 1~3, the integer that b is 1~3, p b/a, n²³It is 1~4 Integer, n²¹For 0~8 integer, n²²It is 0 or 1, Z²¹It for transition metal and is the III group of the periodic table of elements, IV race or V race member Element；

X²¹For O, S, carbon atom number be 1~10 alkylidene, carbon atom number be 1~10 halogeno alkylen, carbon atom number be 6~ The halogenated arlydene that 20 arlydene or carbon atom number is 6~20；Wherein, the alkylidene, halogeno alkylen, arlydene, with And halogenated arlydene works as n in its structure with or without substituent group, hetero atom²²For 1 and n²³N when being 2~4²³A X²¹That This is bonded or is not bonded；

L²¹For halogen atom, cyano, carbon atom number be 1~10 alkyl, carbon atom number be 1~10 halogenated alkyl, carbon atom number For 6~20 aryl, carbon atom number be 6~20 halogenated aryl or-Z²³Y²³；Wherein, the alkylidene, halogeno alkylen, Arlydene and halogenated arlydene work as n in its structure with or without substituent group, hetero atom²¹N when being 2~8²¹A L²¹ It bonds together to form ring or not bond together to form ring；

Y²¹、Y²²And Z²³It is independently of one another O, S, NY²⁴, alkyl or fluoro alkyl；Y²³And Y²⁴Be independently of one another H, F, the aryl or carbon that halogenated alkyl that carbon atom number is 1~10 alkyl, carbon atom number are 1~10, carbon atom number are 6~20 The halogenated aryl that atomicity is 6~20；Wherein, the alkyl, halogenated alkyl, aryl and halogenated aryl have in its structure Have or do not have substituent group, hetero atom, when there are multiple Y²³Or Y²⁴When bond together to form ring or not bond together to form ring.

2. electrolyte according to claim 1, wherein

The fluoro carbonic ester is selected from by the fluoro saturated cyclic carbonic ester and fluoro chain carbon in addition to additive (II) At least one of the group of acid esters composition.

3. electrolyte according to claim 1 or 2, wherein

The additive is selected from the group being made of additive (I), additive (III), additive (IV) and additive (V) At least one of.

4. electrolyte according to claim 1 or 2, wherein

The fluoro carbonic ester is fluorinated chain carbonate, and the additive is additive (II).

5. a kind of electrochemical appliance, which is characterized in that

Has electrolyte described in claim 1,2,3 or 4.

6. a kind of lithium ion secondary battery, which is characterized in that

Has electrolyte described in claim 1,2,3 or 4.

7. a kind of component, which is characterized in that

Have electrochemical appliance described in claim 5 or lithium ion secondary battery as claimed in claim 6.